Photoresist compositions comprising polycyclic polymers with acid labile pendant groups

ABSTRACT

The present invention relates to a radiation sensitive photoresist composition comprising a photoacid initiator and a polycyclic polymer comprising repeating units that contain pendant acid labile groups. Upon exposure to an imaging radiation source the photoacid initiator generates an acid which cleaves the pendant acid labile groups effecting a polarity change in the polymer. The polymer is rendered soluble in an aqueous base in the areas exposed to the imaging source.

BACKGROUND OF THE INVENTION

[0001] 1. Technical Field

[0002] The present invention is related to polycyclic polymers andmethods for their use as photoresists in the manufacture of integratedcircuits. More specifically, the invention is directed to photoresistcompositions comprising a polycyclic polymer and a cationicphotoinitiator. The polycyclic polymer contains recurring acid labilegroups that are pendant from the polymer backbone. The acid labilegroups can be selectively cleaved to form recurring polar groups alongthe backbone of the polymer. The polymers are transparent to short wavelengths of imaging radiation and exhibit resistance to reactive ionetching.

[0003] 2. Background

[0004] Integrated circuits (IC's) are paramount in the manufacture of anarray of electronic devices. They are fabricated from the sequentialformation of alternating and interconnecting bands of conductive,semiconductive and nonconductive layers on an appropriate substrate(e.g., silicon wafer) that are selectively patterned to form circuitsand interconnections to produce specific electrical functions. Thepatterning of IC's is carried out according to various lithographytechniques known in the art. Photolithography employing ultraviolet (UV)light and increasingly deep UV light or other radiation is a fundamentaland important technology utilized in the production of IC devices. Aphotosensitive polymer film (photoresist) is applied over the wafersurface and dried. A photomask containing the desired patterninginformation is then placed in close proximity to the photoresist film.The photoresist is irradiated through the overlying photomask by one ofseveral types of imaging radiation including UV light, e beam electrons,x-rays, or ion beam. Upon exposure to radiation, the photoresistundergoes a chemical change with concomitant changes in solubility.After irradiation, the wafer is soaked in a solution that develops(i.e., selectively removes either the exposed or unexposed regions) thepatterned images in the photosensitive polymer film. Depending on thetype of polymer used, or the polarity of the developing solvent, eitherthe exposed or nonexposed areas of film are removed in the developingprocess to expose the underlying substrate, after which the patternedexposed or unwanted substrate material is removed or changed by anetching process leaving the desired pattern in a functional layer of thewafer. Etching is accomplished by plasma etching, sputter etching, andreactive ion etching (RIE). The remaining photoresist material functionsas a protective barrier against the etching process. Removal of theremaining photoresist material gives the patterned circuit.

[0005] In the manufacture of patterned IC devices, the processes ofetching different layers on the wafer are among the most crucial stepsinvolved. One method is to immerse the substrate and patterned resist ina chemical bath which attacks the exposed substrate surfaces whileleaving the resist itself intact. This “wet” chemical process suffersfrom the difficulty of achieving well defined edges on the etchedsurfaces. This is due to chemical undercutting of the resist materialand the formation of an isotropic image. In other words, conventionalchemical processes do not provide the selectivity of direction(anisotropy) considered necessary to achieve optimum dimensionalspecifications consistent with current processing requirements. Inaddition, the wet processes suffer because of the undesirableenvironmental and safety ramifications.

[0006] Various “dry” processes have been developed to overcome thedrawbacks of the wet chemical process. Such dry processes generallyinvolve passing a gas through a chamber and ionizing the gas by applyinga potential across two electrodes in the presence of the gas. The plasmacontaining the ionic species generated by the potential is used to etcha substrate placed in the chamber. The ionic species generated in theplasma are directed to the exposed substrate where they interact withthe surface material forming volatile products that are removed from thesurface. Typical examples of dry etching are plasma etching, sputteretching and reactive ion etching.

[0007] Reactive ion etching provides well defined vertical sidewallprofiles in the substrate as well as substrate to substrate etchinguniformity. Because of these advantages, the reactive ion etchingtechnique has become the standard in IC manufacture.

[0008] Two types of photoresists are used in the industry, negative andpositive photoresists. Negative resists, upon exposure to imagingradiation, polymerize, crosslink, or change solubility characteristicssuch that the exposed regions are insoluble to the developer. Unexposedareas remain soluble and are washed away. Positive resists function inthe opposite way, becoming soluble in the developer solution afterexposure to imaging radiation.

[0009] One type of positive photoresist material is based uponphenol-formaldehyde novolac polymers. A particular example is thecommercially utilized Shipley AZ1350 material which comprises anm-cresol formaldehyde novolak polymer composition and a diazoketone(2-diazo-1-napthol-5-sulphonic acid ester). When exposed to imagingradiation, the diazoketone is converted to a carboxylic acid, which inturn converts the phenolic polymer to one that is readily soluble inweak aqueous base developing agent.

[0010] U.S. Pat. No. 4,491,628 to Ito et al. discloses positive andnegative photoresist compositions with acid generating photoinitiatorsand polymers with acid labile pendant groups. Because each acidgenerated causes deprotection of multiple acid labile groups thisapproach is known as chemical amplification which serves to increase thequantum yield of the overall photochemical process. The disclosedpolymers include vinylic polymers such as polystyrenes,polyvinylbenzoates, and polyacrylates that are substituted withrecurrent pendant groups that undergo acidolysis to produce productsthat differ in solubility than their precursors. The preferred acidlabile pendant groups include t-butyl esters of carboxylic acids andt-butyl carbonates of phenols. The photoresist can be made positive ornegative depending on the nature of the developing solution employed.

[0011] Trends in the electronics industry continually require IC's thatare faster and consume less power. To meet this specification the ICmust be made smaller. Conducting pathways (i.e., lines) must be madethinner and placed closer together. The significant reduction in thesize of the transistors and the lines produced yields a concomitantincrease in the efficiency of the IC, e.g., greater storage andprocessing of information on a computer chip. To achieve thinner linewidths, higher photoimaging resolution is necessary. Higher resolutionsare possible with shorter wave lengths of the exposure source employedto irradiate the photoresist material. However, the prior artphotoresists such as the phenol-formaldehyde novolac polymers and thesubstituted styrenic polymers contain aromatic groups that inherentlybecome increasingly absorptive as the wave length of light falls belowabout 300 nm, (ACS Symposium Series 537, Polymers for Microelectronics,Resists and Dielectrics, 203rd National Meeting of the American ChemicalSociety, Apr. 5-10, 1992, p.2-24; Polymers for Electronic and PhotonicApplications, Edited by C. P. Wong, Academic Press, p. 67-118). Shorterwave length sources are typically less bright than traditional sourceswhich necessitate a chemical amplification approach using photoacids.The opacity of these aromatic polymers to short wave length light is adrawback in that the photoacids below the polymer surface are notuniformly exposed to the light source and, consequently, the polymer isnot developable. To overcome the transparency deficiencies of thesepolymers, the aromatic content of photoresist polymers must be reduced.If deep UV transparency is desired (i.e., for 248 nm and particularly193 nm wave length exposure), the polymer should contain a minimum ofaromatic character.

[0012] U.S. Pat. No. 5,372,912 concerns a photoresist compositioncontaining an acrylate based copolymer, a phenolic type binder, and aphotosensitive acid generator. The acrylate based copolymer ispolymerized from acrylic acid, alkyl acrylate or methacrylate, and amonomer having an acid labile pendant group. While this composition issufficiently transparent to UV radiation at a wave length of about 240nm, the use of aromatic type binders limits the use of shorter wavelength radiation sources. As is common in the polymer art, theenhancement of one property is usually accomplished at the expense ofanother. When employing acrylate based polymers, the gain intransparency to shorter wave length UV is achieved at the expense ofsacrificing the resist's resistance to the reactive ion etch process.

[0013] In many instances, the improvement in transparency to short wavelength imaging radiation results in the erosion of the resist materialduring the subsequent dry etching process. Because photoresist materialsare generally organic in nature and substrates utilized in themanufacture of IC's are typically inorganic, the photoresist materialhas an inherently higher etch rate than the substrate material whenemploying the RIE technique. This necessitates the need for thephotoresist material to be much thicker than the underlying substrate.Otherwise, the photoresist material will erode away before theunderlying substrate could be fully etched. It follows that lower etchrate resist materials can be employed in thinner layers over thesubstrate to be etched. Thinner layers of resist material allow forhigher resolution which, ultimately, allows for narrower conductivelines and smaller transistors.

[0014] J. V. Crivello et al. (Chemically Amplified Electron-BeamPhotoresists, Chem. Mater., 1996, 8, 376-381) describe a polymer blendcomprising 20 weight % of a free radically polymerized homopolymer of anorbornene monomer bearing acid labile groups and 80 weight % of ahomopolymer of 4-hydroxy-α-methylstyrene containing acid labile groupsfor use in electron-beam photoresists. As discussed supra, the increasedabsorbity (especially in high concentrations) of aromatic groups rendersthese compositions opaque and unusable for short wave length imagingradiation below 200 nm.

[0015] The disclosed compositions are suitable only for electron-beamphotoresists and can not be utilized for deep UV imaging (particularlynot for 193 nm resists).

[0016] Crivello et al. investigated blend compositions because theyobserved the oxygen plasma etch rate to be unacceptably high for freeradically polymerized homopolymers of norbornene monomers bearing acidlabile groups.

[0017] Accordingly, there is a need for a photoresist composition whichis compatible with the general chemical amplification scheme andprovides transparency to short wave length imaging radiation while beingsufficiently resistant to a reactive ion etching processing environment.

SUMMARY OF THE INVENTION

[0018] It is a general object of the invention to provide a photoresistcomposition comprising a polycyclic polymer backbone having pendant acidlabile groups and a photoinitiator.

[0019] It is another object of the invention to provide polycyclicpolymers that have recurrent pendant acid labile groups that can becleaved to form polar groups.

[0020] It is still another object of the invention to provide polymercompositions that are transparent to short wave length imagingradiation.

[0021] It is a further object of the invention to provide polymercompositions that are resistant to dry etching processes.

[0022] It is a still further object of the invention to provide polymercompositions that are transparent to short wave length imaging radiationand are resistant to dry etching processes.

[0023] It is yet another object of the invention to provide polycyclicmonomers that contain acid labile pendant groups that can be polymerizedto form polymers amenable to aqueous base development.

[0024] These and other objects of the invention are accomplished bypolymerizing a reaction mixture comprising an acid labile groupfunctionalized-polycycloolefinic monomer, a solvent, a single ormulticomponent catalyst system each containing a Group VIII metal ionsource. In the multicomponent catalyst systems of the invention theGroup VIII ion source is utilized in combination with one or both of anorganometal cocatalyst and a third component. The single andmulticomponent catalyst systems can be utilized with an optional chaintransfer agent (CTA) selected from a compound having a terminal olefinicdouble bond between adjacent carbon atoms, wherein at least one of saidadjacent carbon atoms has two hydrogen atoms attached thereto. The CTAis selected from unsaturated compounds that are typically cationicallynon-polymerizable and, therefore, exclude styrenes, vinyl ethers, andconjugated dienes.

[0025] The polymers obtained are useful in photoresist compositions thatinclude a radiation-sensitive acid generator.

DETAILED DESCRIPTION

[0026] The present invention relates to a radiation-sensitive resistcomposition comprising an acid-generating initiator and a polycyclicpolymer containing recurring acid labile pendant groups along thepolymer backbone. The polymer containing the initiator is coated as athin film on a substrate, baked under controlled conditions, exposed toradiation in a patterned configuration, and optionally post baked undercontrolled conditions to further promote the deprotection. In theportions of the film that have been exposed to radiation, the recurrentacid labile pendant groups on the polymer backbone are cleaved to formpolar recurring groups. The exposed areas so treated are selectivelyremoved with an alkaline developer. Alternatively, the unexposed regionsof the polymer remain nonpolar and can be selectively removed bytreatment with a suitable nonpolar solvent for a negative tonedevelopment. Image reversal can easily be achieved by proper choice ofdeveloper owing to the difference in the solubility characteristics ofthe exposed and unexposed portions of the polymer.

[0027] The polymers of the present invention comprisepolycyclic-repeating units, a portion of which are substituted with acidlabile groups. The instant polymers are prepared by polymerizing thepolycyclic monomers of this invention. By the term “polycyclic”(norbornene-type or norbornene-functional) is meant that the monomercontains at least one norbornene moiety as shown below:

[0028] The simplest polycyclic monomer of the invention is the bicyclicmonomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene.The acid labile functionality is introduced into the polymer chain bypolymerizing a reaction medium comprising one or more acid labilesubstituted polycyclic monomers set forth under Formula I below inoptional combination with one or more polycyclic monomers set forthunder Formulae II, III, IV, and V below in the presence of the GroupVIII metal catalyst system.

Monomers

[0029] The acid labile polycyclic monomers useful in the practice of thepresent invention are selected from a monomer represented by the formulabelow:

[0030] wherein R¹ to R⁴ independently represent a substituent selectedfrom the group —(CH₂)_(n)C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)C(O)R and —(CH₂)_(n)—OC(O)OR,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂ subjectto the proviso that at least one of R¹ to R⁴ is selected from the acidlabile group —(CH₂)_(n)C(O)OR*, R represents hydrogen, linear andbranched (C₁ to C₁₀) alkyl, and m is an integer from 0 to 5, and n is aninteger from 0 to 10, preferably n is 0. R* represents moieties (i.e.,blocking or protecting groups) that are cleavable by photoacidinitiators selected from —C(CH₃)₃, —Si(CH₃)₃, isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahrydropyranoyl,3-oxocyclohexanonyl, mevalonic lactonyl, dicyclopropylmethyl (Dcpm), anddimethylcyclopropylmethyl (Dmcp) groups. R** independently represents Rand R* as defined above. The Dcpm and Dmcp groups are respectivelyrepresented by the following structures:

[0031] Polycyclic monomers of the above formula with a substituentselected from the group —(CH₂)_(n)C(R)₂CH(R)(C(O)OR**) or—(CH₂)_(n)C(R)₂CH(C(O)OR**)₂ can be represented as follows:

[0032] In the above formulae m is preferably 0 or 1, more preferably mis 0. When m is 0 the preferred structures are represented below:

[0033] wherein R¹ to R⁴are previously defined.

[0034] It should be apparent to those skilled in the art that anyphotoacid cleavable moiety is suitable in the practice of the inventionso long as the polymerization reaction is not substantially inhibited bysame.

[0035] The preferred acid labile groups are the organic ester groupswhich undergo a cleavage reaction in the presence of an acid. Preferredacid labile groups include ester groups and carbonate groups. Thet-butyl esters of carboxylic acids are especially preferred.

[0036] The monomers described under Formula I, when polymerized into thepolymer backbone, provide recurring pendant acid sensitive groups thatare subsequently cleaved to confer polarity or solubility to thepolymer.

[0037] The optional second monomer is represented by the structure setforth under Formula II below:

[0038] wherein R⁵ to R⁸ independently represent a neutral substituentselected from the group: —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″,—(CH₂)_(n)—OC(O)R″, —(CH₂)—OC(O)OR″, —(CH₂)_(n)—C(O)R″,—(CH₂)_(n)C(R*)₂CH(R*)(C(O)OR*), and —(CH₂)_(n)C(R*)₂CH(C(O)OR*)₂wherein p is an integer from 0 to 5 (preferably 0 or 1, more preferably0) and n is an integer from 0 to 10 (preferably 0). R⁵ to R⁸ canindependently represent hydrogen, linear and branched (C₁ to C₁₀) alkyl,so long as at least one of the remaining R⁵ to R⁸ substituents isselected from one of the neutral groups represented above. Rindependently represents hydrogen and linear and branched (C₁ to C₁₀)alkyl, R″ represents hydrogen, linear and branched (C₁ to C₁₀) alkyl,monocyclic and polycyclic (C₄ to C₂₀) cycloaliphatic moieties, cyclicethers, cyclic keytones, and cyclic esters (lactones). Examples ofcycloaliphatic monocyclic moieties include cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, and the like. Examples of cycloaliphaticpolycyclic moieties include, norbornyl, adamantyl,tetrahrydrodicyclopentadienyl (tricyclo[5.2.1.0^(2,6)] decanyl), and thelike. Examples of cyclic ethers include tetrahydrofuranyl andtetrahrydropyranyl moieties. An example of a cyclic ketone is a3-oxocyclohexanonyl moiety. An example of a cyclic ester or lactone is amevalonic lactonyl moiety.

[0039] The preferred monomers under Formula II are the (C₁ to C₅) alkylesters of the carboxylic acid with the methyl and ethyl estersparticularly preferred. The ester functionalities impart hydrophilicity,promote good wetting of the developer and improve film mechanicalproperties.

[0040] The optional third monomer component is represented by thestructure under Formula III below:

[0041] wherein R⁹ to R¹² independently represent a carboxylicsubstituent selected from the formula —(CH₂)_(n)C(O)OH, wherein q is aninteger from 0 to 5 (preferably 0 or 1, more preferably 0) and n is aninteger from 0 to 10 (preferably 0). R⁹ to R¹² can independentlyrepresent hydrogen, linear and branched (C₁ to C₁₀) alkyl, so long as atleast one of the remaining R⁹ to R¹² substituents is selected from acarboxylic acid group represented above.

[0042] The monomers containing carboxylic acid functionality contributeto the hydrophilicity of the polymer consequently aiding in thedevelopability of the polymer in aqueous base systems at high rates.

[0043] The optional monomers under Formula IV are represented by thestructure below:

[0044] wherein R¹³ to R¹⁶ independently represent linear or branched (C₁to C₁₀) alkyl and r is an integer from 0 to 5 (preferably 0 or 1, morepreferably 0). Any of R¹³ to R¹⁶ can represent hydrogen so long as atleast one of the remaining R¹³ to R¹⁶ substituents is selected from analkyl group set defined above. Of the above alkyl substituents, decyl isespecially preferred.

[0045] The polymerization of alkyl substituted monomers into the polymerbackbone is a method to control the Tg of the polymer as disclosed inU.S. Pat. No. 5,468,819 to Goodall et al.

[0046] An economical route for the preparation of the functional orhydrocarbyl substituted polycyclic monomers of the invention relies onthe Diels-Alder reaction in which cyclopentadiene (CPD) or substitutedCPD is reacted with a suitably substituted dienophile at elevatedtemperatures to form a substituted polycyclic adduct generally shown bythe following reaction scheme:

[0047] Other polycyclic adducts can be prepared by the thermal pyrolysisof dicyclopentadiene (DCPD) in the presence of a suitable dienophile.The reaction proceeds by the initial pyrolysis of DCPD to CPD followedby the Diels-Alder addition of CPD and the dienophile to give theadducts as shown below:

[0048] wherein R′ to R″″ independently represents the substituentsdefined under R¹ to R¹⁶ in Formulae I, II, III, and IV above.

[0049] For example the 2-norbornene-5-carboxylic acid(bicyclo[2.2.1]hept-5-ene-2-caboxylylic acid) can be prepared by theDiels-Alder reaction of cyclopentadiene with acrylic acid in accordancewith the following reaction scheme:

[0050] The corresponding t-butyl ester of the carboxylic acid can beprepared by reacting the carboxylic acid functionality with isobutylenein the presence of triflic acid at reduced temperatures (i.e., −30 to−20° C.) as shown in the reaction scheme below:

[0051] Another more preferred route to the t-butyl ester of thenorbornene carboxylic acid involves the Diels-Alder reaction ofcyclopentadiene with t-butyl acrylate.

[0052] Another synthesis route to the acid and ester substitutedmonomers of the present invention is through an ortho ester substitutedpolycyclic monomer with subsequent hydrolysis to a carboxylicfunctionality or partial hydrolysis to an ester functionality. Thecarboxylic functionality can be esterified to the desired ester Theortho ester substituted monomers of the invention are represented byFormula V below:

[0053] wherein R¹⁷, R¹⁸, and R¹⁹ independently represent a linear orbranched (C₁ to C₅) alkyl group or any R¹⁷, R¹⁸, and R¹⁹ can be takentogether along with the oxygen atoms to which they are attached to forma substituted or unsubstituted 5 to 10 membered cyclic or bicyclic ringcontaining 3 to 8 carbon atoms (excluding substituent groups), s is aninteger from 0 to 5 (preferably 0), and t is an integer from 1 to 5(preferably 1). Representative structures wherein s is 0, t is 1, andR¹⁷, R¹⁸, and R¹⁹ are taken with the oxygen atoms to which they areattached to form a cyclic or bicyclic ring are set forth below:

[0054] wherein R^(17′), R^(18′), and R^(19′) independently representhydrogen and linear and branched (C₁ to C₅) alkyl. The ortho esters ofthe present invention can be synthesized in accordance with theso-called Pinner synthesis (A. Pinner, Chem. Ber., 16, 1643 (1883), andvia the procedure set forth by S. M. McElvain and J. T. Venerable, J.Am. Chem. Soc., 72, 1661 (1950); S M. McElvain and C. L. Aldridge, J.Am. Chem. Soc.,75, 3987 (1953). A typical synthesis is set forth in thereaction scheme below:

[0055] An alternative synthesis route wherein an alkyl acrylate istreated with a trialkyloxonium tetrafluoroborate salt followed by analkali metal (sodium alcoholate) to yield the trialkoxymethyl orthoester (H. Meerwein, P. Borner, O. Fuchs, H. J. Sasse, H. Schrodt, and J.Spille, Chem. Ber., 89, 2060 (1956).

[0056] As discussed above the otho ester can undergo a hydrolysisreaction in the presence of dilute acid catalysts such as hydrobromic,hydroiodic, and acetic acid to yield the carboxylic acid. The carboxylicacid can in turn be esterified in the presence of an aliphatic alcoholand an acid catalyst to yield the respective ester. It should berecognized that in the case of polycyclic monomers that are di- ormulti-substituted with ortho ester groups that the ortho ester moietiescan be partially hydrolyzed to yield the acid and a conventional esteron the same monomer as illustrated below:

[0057] Another and more preferred route to difunctional polycyclicmonomers is through the hydrolysis and partial hydrolysis of nadicanhydride (endo-5-norbornene-2,3-dicarboxylic anhydride). Nadicanhydride can be filly hydrolyzed to the dicarboxylic acid or partiallyhydrolyzed to the an acid and ester functionality or diesterfunctionality as shown below:

[0058] wherein R¹⁷ independently represents linear and branched (C₁ toC₅) alkyl. Preferably R¹⁷ is methyl, ethyl, or t-butyl. In a preferredsynthesis the nadic anhydride staring material is the exo-isomer. Theexo-isomer is easily prepared by heating the endo-isomer at 190° C.followed by recrystallization from an appropriate solvent (toluene). Toobtain the diacid under reaction scheme 1, nadic anhydride is simplyhydrolyzed in boiling water to obtain almost a quantitative yield of thediacid product. The mixed carboxylic acid—alkyl ester functionalityshown in scheme 3 is obtained by heating nadic anhydride under refluxfor 3 to 4 hours in the presence of the appropriate aliphatic alcohol(R¹⁷OH). Alternatively, the same product can be prepared by firstreacting the nadic anhydride starting material with an aliphatic alcoholand trialkyl amine followed by treatment with dilute HCl. The diesterproduct substituted with identical alkyl (R¹⁷) groups can be preparedfrom the diacid by reacting the diacid with a triallyloxoniumtetrafluoroborate, e.g., R¹⁷ ₃O[BF₄], in methylene chloride at ambienttemperature, in the presence of diisopropylethylamine. To obtain esterswith differing R¹⁷ alkyl groups the mixed acid—ester product obtained inscheme 3 is employed as the starting material. In this embodiment theacid group is esterified as set forth in reaction scheme 2. However, atrialkyloxonium tetrafluoroborate having a differing alkyl group thanthe alkyl group already present in the ester functionality is employed.

[0059] It should be noted that the foregoing monomers containing theprecursor functionalities can be converted to the desired functionalgroups before they are polymerized or the monomers can be firstpolymerized and then the respective polymers containing the precursorfunctional substituents can then be post reacted to give the desiredfunctionality.

[0060] It is contemplated within the scope of this invention that themonomers described under Formulae I to V wherein m, p. q, r, and s is 0the methylene bridge unit can be replaced by oxygen to give7-oxo-norbornene derivatives.

[0061] It is also contemplated that for applications at 248 nm wavelength and above R⁵ to R¹⁶ and R¹¹ in Formulae I, III, and IV can bearomatic such as phenyl.

Polymers

[0062] One or more of the acid labile substituted polycyclic monomersdescribed under Formula I can be polymerized alone or in combinationwith one or more of the polycyclic monomers described under Formulae II,V, IV, and V. It is also contemplated that the polycyclic monomers ofFormulae I to V can be copolymerized with carbon monoxide to affordalternating copolymers of the polycyclic and carbon monoxide. Copolymersof norbornene having pendant carboxylic acid groups and carbon monoxidehave been described in U.S. Pat. No. 4,960,857 the disclosure of whichis hereby incorporated by reference. The monomers of Formulae I to V andcarbon monoxide can be copolymerized in the presence of a palladiumcontaining catalyst system as described in Chem. Rev. 1996, 96, 663-681.It should be readily understood by those skilled in the art that thealternating copolymers of polycyclic/carbon monoxide can exist in eitherthe keto or spiroketal isomeric form. Accordingly, the present inventioncontemplates homopolymers and copolymers containing random repeatingunits derived (polymerized) from a monomer or monomers represented byFormula I, copolymers containing random repeating units derived(polymerized) from a monomer(s) represented by Formula I in optionalcombination with any monomer(s) represented by Formulae H to V. Inaddition, the present invention contemplates alternating copolymerscontaining repeating units derived (polymerized) from carbon monoxideand a monomer(s) represented by Formulae I to V.

[0063] The polymers of the present invention are the key ingredient ofthe composition. The polymer will generally comprise about 5 to 100 mole% of the monomer (repeating unit) that contains the acid labile groupcomponent. Preferably the polymer contains about 20 to 90 mole % of themonomer that contains the acid labile group. More preferably the polymercontains about 30 to 70 mole % of the monomeric unit that contains theacid labile functionality. The remainder of polymer composition is madeup of repeating units polymerized from the optional monomers set forthabove under Formulae II to V. The choice and the amount of specificmonomers employed in the polymer can be varied according to theproperties desired. For example, by varying the amount of carboxylicacid functionality in the polymer backbone, the solubility of thepolymer to various developing solvents can be adjusted as desired.Monomers containing the ester functionality can be varied to enhance themechanical properties of the polymer and radiation sensitivity of thesystem. Finally, the glass transition temperature properties of thepolymer can be adjusted by incorporating cyclic repeating units thatcontain long chain alkyl groups such as decyl.

[0064] There are several routes to polymerize cyclic olefin monomerssuch as norbornene and higher cyclic (polycyclic) monomers containingthe norbornene moiety. These include: (1) ring-opening metathesispolymerization (ROMP); (2) ROMP followed by hydrogenation; and (3)addition polymerization. Each of the foregoing routes produces polymerswith specific structures as shown in the diagram 1 below:

Diagram 1

[0065]

[0066] A ROMP polymer has a different structure than that of an additionpolymer. A ROMP polymer contains a repeat unit with one less cyclic unitthan did the string monomer. The repeat units are linked together in anunsaturated backbone as shown above. Because of this unsaturation thepolymer preferably should subsequently be hydrogenated to conferoxidative stability to the backbone. Addition polymers on the other handhave no C═C unsaturation in the polymer backbone despite being formedfrom the same monomer.

[0067] The monomers of this invention can be polymerized by additionpolymerization and by ring-opening metathesis polymerization (ROMP)preferably with subsequent hydrogenation. The cyclic polymers of thepresent invention are represented by the following structures:

[0068] wherein R′ to R″″ independently represents R¹ to R¹⁹ as definedin Formulae I to V above, m is an integer from 0 to 5 and a representsthe number of repeating units in the polymer backbone.

[0069] The ROMP polymers of the present invention are polymerized in thepresence of a metathesis ring-opening polymerization catalyst in anappropriate solvent. Methods of polymerizing via ROMP and the subsequenthydrogenation of the ring-opened polymers so obtained are disclosed inU.S. Pat. Nos. 5,053,471 and 5,202,388 which are incorporated herein byreference.

[0070] In one ROMP embodiment the polycyclic monomers of the inventioncan be polymerized in the presence of a single component ruthenium orosmium metal carbene complex catalyst such as those disclosed in WO95-US9655. The monomer to catalyst ratio employed should range fromabout 100:1 to about 2,000:1, with a preferred ratio of about 500:1. Thereaction can be conducted in halohydrocarbon solvent such asdichloroethane, dichloromethane, chlorobenzene and the like or in ahydrocarbon solvent such as toluene. The amount of solvent employed inthe reaction medium should be sufficient to achieve a solids content ofabout 5 to about 40 weight percent, with 6 to 25 weight percent solidsto solvent being preferred. The reaction can be conducted at atemperature ranging from about 0° C. to about 60° C., with about 20° C.to 50° C. being preferred.

[0071] A preferred metal carbene catalyst isbis(tricyclohexylphosphine)benzylidene ruthenium. Surprisingly andadvantageously, it has been found that this catalyst can be utilized asthe initial ROMP reaction catalyst and as an efficient hydrogenationcatalyst to afford an essentially saturated ROMP polymer. No additionalhydrogenation catalyst need be employed. Following the initial ROMPreaction, all that is needed to effect the hydrogenation of the polymerbackbone is to maintain hydrogen pressure over the reaction medium at atemperature above about 100° C. but lower than about 220° C., preferablybetween about 150 to about 200° C.

[0072] The addition polymers of the present invention can be preparedvia standard free radical solution polymerization methods that arewell-known by those skilled in the art. The monomer of Formulae I to Vcan be homopolymerized or copolymerized in the presence of maleicanhydride. Free radical polymerization techniques are set forth in theEncyclopedia of Polymer Science, John Wiley & Sons, 13, 708 (1988).

[0073] Alternatively, and preferably, the monomers of this invention arepolymerized in the presence of a single or multicomponent catalystsystem comprising a Group VIII metal ion source (preferably palladium ornickel). Surprisingly, it has been found that the addition polymers soproduced possess excellent transparency to deep UV light (193 nm) andexhibit excellent resistance to reactive ion etching.

[0074] The preferred polymers of this invention are polymerized fromreaction mixtures comprising at least one polycyclic monomer selectedfrom Formula I, a solvent, a catalyst system containing a Group VIIImetal ion source, and an optional chain transfer agent. The catalystsystem can be a preformed single component Group VIII metal basedcatalyst or a multicomponent Group VIII metal catalyst.

Single Component Systems

[0075] In one embodiment, the single component catalyst system of thisinvention comprises a Group VIII metal cation complex and a weaklycoordinating counteranion as represented by the following formula:

[0076] wherein L represents a ligand containing 1, 2, or 3 π-bonds; Mrepresents a Group VIII transition metal; X represents a ligandcontaining 1 σ-bond and between 0 to 3 π-bonds; y is 0, 1, or 2 and z is0 or 1 and wherein y and z cannot both be 0 at the same time, and when yis 0, a is 2 and when y is 1, a is 1; and CA is a weakly coordinatingcounteranion.

[0077] The phrase “weakly coordinating counteranion” refers to an anionwhich is only weakly coordinated to the cation, thereby remainingsufficiently labile to be displaced by a neutral Lewis base. Morespecifically the phrase refers to an anion which when functioning as astabilizing anion in the catalyst system of this invention does nottransfer an anionic substituent or fragment thereof to the cation,thereby forming a neutral product. The counteranion is non-oxidative,non-reducing, non-nucleophilic, and relatively inert.

[0078] L is a neutral ligand that is weakly coordinated to the GroupVIII metal cation complex. In other words, the ligand is relativelyinert and is readily displaced from the metal cation complex by theinserting monomer in the growing polymer chain. Suitable π-bondcontaining ligands include (C₂ to C₁₂) monoolefinic (e.g.,2,3-dimethyl-2-butene), dioolefinic (C₄ to C₁₂) (e.g., norbornadiene)and (C₆ to C₂₀) aromatic moieties. Preferably ligand L is a chelatingbidentate cyclo(C₆ to C₁₂) diolefin, for example cyclooctadiene (COD) ordibenzo COD, or an aromatic compound such as benzene, toluene, ormesitylene.

[0079] Group VIII metal M is selected from Group VIII metals of thePeriodic Table of the Elements. Preferably M is selected from the groupconsisting of nickel, palladium, cobalt, platinum, iron, and ruthenium.The most preferred metals are nickel and palladium.

[0080] Ligand X is selected from (i) a moiety that provides a singlemetal-carbon σ-bond (no π bonds) to the metal in the cation complex or(ii) a moiety that provides a single metal carbon σ-bond and 1 to 3π-bonds to the metal in the cation complex. Under embodiment (i) themoiety is bound to the Group VIII metal by a single metal-carbon σ-bondand no π-bonds. Representative ligands defined under this embodimentinclude (C₁ to C₁₀) alkyl moieties selected from methyl, ethyl, linearand branched moieties such as propyl, butyl, pentyl, neopentyl, hexyl,heptyl, octyl, nonyl and decyl and (C₇ to C₁₅) aralkyl such as benzyl.Under embodiment (ii) generally defined above, the cation has ahydrocarbyl group directly bound to the metal by a single metal-carbonσ-bond, and also by at least one, but no more than three π-bonds. Byhydrocarbyl is meant a group that is capable of stabilizing the GroupVIII metal cation complex by providing a carbon-metal σ-bond and one tothree olefinic σ-bonds that may be conjugated or non-conjugated.Representative hydrocarbyl groups are (C₃ to C₂₀) alkenyl which may benon-cyclic, monocyclic, or polycyclic and can be substituted with linearand branched (C₁ to C₂₀) alkoxy, (C₆ to C₁₅) aryloxy or halo groups(e.g., Cl and F).

[0081] Preferably X is a single allyl ligand, or, a canonical formthereof, which provides a σ-bond and a π-bond; or a compound providingat least one olefinic π-bond to the metal, and a σ-bond to the metalfrom a distal carbon atom, spaced apart from either olefinic carbon atomby at least two carbon-carbon single bonds (embodiment iii).

[0082] It should be readily apparent to those skilled in the art thatwhen ligand L or X is absent (i.e., y or z is zero), the metal cationcomplex will be weakly ligated by the solvent in which the reaction wascarried out. Representative solvents include but are not limited tohalogenated hydrocarbons such as carbon tetrachloride, chloroform,dichloromethane, 1,2-dichloroethane and aromatic solvents such asbenzene, toluene, mesitylene, chlorobenzene, and nitrobenzene, and thelike. A more detailed discussion on appropriate solvents will follow.

[0083] Selected embodiments of the Group VIII metal cation complexes ofthe single component catalyst systems of this invention are shown below.

[0084] Structure VII illustrates embodiment (i) wherein ligand X is amethyl group that is bound to the metal via a single metal-carbonσ-bond, and ligand L is COD that is weakly coordinated to the palladiummetal via two olefinic π-bonds. In the structure below M preferablyrepresents palladium or nickel.

[0085] Structures VIII, IX and X illustrate various examples ofembodiment (ii) wherein X is an allyl group that is bound to the metal(palladium is shown for illustrative purposes only) via a singlemetal-carbon σ-bond and at least one but no more than three π-bonds.

[0086] In Structure VIII, L is not present but an aromatic groupproviding three π-bonds is weakly coordinated to the palladium metal; Xis an allyl group providing a single metal-carbon σ-bond and an olefinicπ-bond to the palladium.

[0087] In Structure IX, L is COD and X is an allyl group providing ametal-carbon σ-bond and an olefinic π-bond to the palladium.

[0088] Structure X illustrates an embodiment wherein ligand X is anunsaturated hydrocarbon group that provides a metal-carbon σ-bond, aconjugated π-bond and two additional π-bonds to the palladium; L isabsent.

[0089] Substituents R²⁰, R²¹, R²² will be described in detail below.

[0090] Structures XI and XII illustrate examples of embodiment (iii)wherein L is COD and X is a ligand that provides at least one olefinicπ-bond to the Group VIII metal and a σ-bond to the metal from a distalcarbon atom, spaced apart from either olefinic carbon atom by at leasttwo carbon-carbon single bonds.

[0091] The above-described Group VIII cation complexes are associatedwith a weakly coordinating or non-coordinating counteranion, CA⁻, whichis relatively inert, a poor nucleophile and provides the cation complexwith essential solubility in the reaction solvent. The key to properanion design requires that it be labile, and stable and inert towardreactions with the cationic Group VIII metal complex in the finalcatalyst species and that it renders the single component catalystsoluble in the solvents of this invention. The anions which are stabletoward reactions with water or Brønsted acids, and which do not haveacidic protons located on the exterior of the anion (i.e., anioniccomplexes which do not react with strong acids or bases) possess thestability necessary to qualify as a stable anion for the catalystsystem. The properties of the anion which are important for maximumlability include overall size, and shape (i.e., large radius ofcurvature), and nucleophilicity.

[0092] In general, a suitable anion may be any stable anion which allowsthe catalyst to be dissolved in a solvent of choice, and has thefollowing attributes: (1) the anion should form stable salts with theaforementioned Lewis acid, Brønsted acids, reducible Lewis Acids,protonated Lewis bases, thallium and silver cations; (2) the negativecharge on the anion should be delocalized over the framework of theanion or be localized within the core of the anion; (3) the anion shouldbe a relatively poor nucleophile; and (4) the anion should not be apowerful reducing or oxidizing agent.

[0093] Anions that meet the foregoing criteria can be selected from thegroup consisting of a tetrafluoride of Ga, Al, or B; a hexafluoride ofP, Sb, or As; perfluoro-acetates, propionates and butyrates, hydratedperchlorate; toluene sulfonates, and trifluoromethyl sulfonate; andsubstituted tetraphenyl borate wherein the phenyl ring is substitutedwith fluorine or trifluoromethyl moieties. Selected examples ofcounteranions include BF₄ ⁻; PF₆ ⁻, AlF₃O₃SCF₃ ⁻, SbF₆ ⁻, SbF₅SO₃F⁻,AsF₆ ⁻, trifluoroacetate (CF₃CO₂ ⁻), pentafluoropropionate (C₂F₅CO₂ ⁻),heptafluorobutyrate (CF₃CF₂CF₂CO₂ ⁻), perchlorate (ClO₄ ⁻.H₂O),p-toluene-sulfonate (p-CH₃C₆H₄SO₃ ⁻) and tetraphenyl borates representedby the formula:

[0094] wherein R″ independently represents hydrogen, fluorine andtrifluoromethyl and n is 1 to 5.

[0095] A preferred single component catalyst of the foregoing embodimentare represented by the formula:

[0096] The catalyst comprises a π-allyl Group VIII metal complex with aweakly coordinating counteranion. The allyl group of the metal cationcomplex is provided by a compound containing allylic functionality whichfunctionality is bound to the M by a single carbon-metal σ-bond and anolefinic π-bond. The Group VIII metal M is preferably selected fromnickel and palladium with palladium being the most preferred metal.Surprisingly, it has been found that these single component catalystswherein M is palladium and the cation complex is devoid of ligands otherthan the allyl functionality (i.e., L_(y)=0), exhibit excellent activityfor the polymerization of functional polycyclic monomers such as thesilyl containing monomers of this invention. As discussed above, it willbe understood that the catalysts are solvated by the reaction diluentwhich diluent can be considered very weak ligands to the Group VIIImetal in the cation complex.

[0097] Substituents R²⁰, R²¹, and R²² on the allyl group set forth abovein Structures VIII, IX and XIII are each independently hydrogen,branched or unbranched (C₁ to C₅) alkyl such as methyl, ethyl, n-propyl,isopropyl, and t-butyl, (C₆ to C₁₄) aryl, such as phenyl and naphthyl(C₇ to C₁₀) aralkyl such as benzyl —COOR¹⁶, —(CH₂)_(n)OR¹⁶, Cl and (C₅to C₆) cycloaliphatic, wherein R¹⁶ is (C₁ to C₅) alkyl such as methyl,ethyl, n-propyl, isopropyl, n-butyl and i-butyl, and n is 1 to 5.

[0098] Optionally, any two of R²⁰, R²¹, and R²² may be linked togetherto form a cyclic- or multi-cyclic ring structure. The cyclic ringstructure can be carbocyclic or heterocyclic. Preferably any two of R²⁰,R²¹, and R²² taken together with the carbon atoms to which they areattached form rings of 5 to 20 atoms. Representative heteroatoms includenitrogen, sulfur and carbonyl. Illustrative of the cyclic groups withallylic functionality are the following structures:

[0099] wherein R²³ is hydrogen, linear or branched (C₁ to C₅) alkyl suchas methyl, ethyl, n-propyl isopropyl, n-butyl, isobutyl, and pentyl, R²⁴is methylcarbonyl, and R²⁵ is linear or branched (C₁ to C₂₀) alkyl.Counteranion CA⁻ is defined as above.

[0100] Additional examples of π-allyl metal complexes are found in R. G.Guy and B. L. Shaw, Advances in Inorganic Chemistry and Radiochemistry,Vol. 4, Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer,M. L. H. Green, R. B. King, R. Köster, P. L. I. Nagy, G. N. Schrauzer,Advances in Organometallic Chemistry, Vol. 2, Academic Press Inc., NewYork, 1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc.,(1964) 1585; and H. C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225;which are all hereby incorporated by reference.

[0101] The single component catalyst of the foregoing embodiment can beprepared by combining a ligated Group VIII metal halide component with asalt that provides the counteranion for the subsequently formed metalcation complex. The ligated Group VIII metal halide component,counteranion providing salt, and optional π-bond containing component,e.g., COD, are combined in a solvent capable of solvating the formedsingle component catalyst. The solvent utilized is preferably the samesolvent chosen for the reaction medium. The catalyst can be preformed insolvent or can be formed in situ in the reaction medium.

[0102] Suitable counteranion providing salts are any salts capable ofproviding the counteranions discussed above. For example, salts ofsodium, lithium, potassium, silver, thallium, and ammonia, wherein theanion is selected from the counteranions (CA⁻) defined previously.Illustrative counteranion providing salts include TIPF₆, AgPF₆, AgSbF₆,LiBF₄, NH₄PF₆, KAsF₆, AgC₂F₅CO₂, AgBF₄ AgCF₃CO₂, AgClO₄.H₂O , AgAsF₆,AgCF₃CF₂CF₂CO₂, AgC₂F₅CO₂, (C₄H₉)₄NB(C₆F₅)₄, and

[0103] The specific catalyst: [allyl-Pd-COD]⁺PF₆ ⁻ is preformed byforming a ligated palladium halide component, i.e., bis(allyl Pdbromide), which is then subjected to scission with a halide abstractingagent in the form of a counteranion providing salt, i.e., TIPF₆ in thepresence of COD. The reaction sequence is written as follows:

[0104] When partitioned, only one COD ligand remains, which is bonded bytwo π-bonds to the palladium. The allyl functionality is bonded by onemetal-carbon σ-bond and one π-bond to the palladium.

[0105] For the preparation of the preferred π-allyl Group VIIImetal/counteranion single component catalysts represented in StructureXIII above, i.e., when M is palladium, allylpalladium chloride iscombined with the desired counteranion providing salt, preferably silversalts of the counteranion, in an appropriate solvent. The chlorideligand comes off the allyl palladium complex as a precipitate of silverchloride (AgCl) which can be filtered out of the solution. Theallylpalladium cation complex/counteranion single component catalystremains in solution. The palladium metal is devoid of any ligands apartfrom the allylic functionality.

[0106] An alternative single component catalyst that is useful in thepresent invention is represented by the formula below:

Pd[R²⁷CN]₄[CA⁻]₂

[0107] wherein R²⁷ independently represents linear and branched (C₁ toC₁₀) alkyl and CA⁻ is a counteranion defined as above.

[0108] Another single component catalyst system useful in makingpolymers utilized in this invention is represented by the formula:

E_(n)Ni(C₆F₅)₂

[0109] wherein n is 1 or 2 and E represents a neutral 2 electron donorligand. When n is 1, E preferably is a π-arene ligand such as toluene,benzene, and mesitylene. When n is 2, E is preferably selected fromdiethylether, tetrahrydrofuran (THF), and dioxane. The ratio of monomerto catalyst in the reaction medium can range from about 2000:1 to about100:1. The reaction can be run in a hydrocarbon solvent such ascyclohexane, toluene, and the like at a temperature range from about 0°C. to about 70° C., preferably 10° C. to about 50° C., and morepreferably from about 20° C. to about 40° C. Preferred catalysts of theabove formula are (toluene)bis(perfluorophenyl) nickel(mesitylene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl)nickel, bis(tetrahrydrofuran)bis(perfluorophenyl) nickel andbis(dioxane)bis(perfluorophenyl) nickel.

Multicomponent Systems

[0110] The multicomponent catalyst system embodiment of the presentinvention comprises a Group VIII metal ion source, in combination withone or both of an organometal cocatalyst and a third component. Thecocatalyst is selected from organoaluminum compounds, dialkylaluminumhydrides, dialkyl zinc compounds, dialkyl magnesium compounds, andalkyllithium compounds.

[0111] The Group VIII metal ion source is preferably selected from acompound containing nickel palladium, cobalt, iron, and ruthenium withnickel and palladium being most preferred. There are no restrictions onthe Group VIII metal compound so long as it provides a source ofcatalytically active Group VIII metal ions. Preferably, the Group VIIImetal compound is soluble or can be made to be soluble in the reactionmedium.

[0112] The Group VIII metal compound comprises ionic and/or neutralligand(s) bound to the Group VIII metal. The ionic and neutral ligandscan be selected from a variety of monodentate, bidentate, ormultidentate moieties and combinations thereof.

[0113] Representative of the ionic ligands that can be bonded to themetal to form the Group VIII compound are anionic ligands selected fromthe halides such as chloride, bromide, iodide or fluoride ions;pseudohalides such as cyanide, cyanate, thiocyanate, hydride; carbanionssuch as branched and unbranched (C₁ to C₄₀) alkylanions, phenyl anions;cyclopentadienylide anions; π-allyl groupings; enolates of β-dicarbonylcompounds such as acetylacetonate (4-pentanedionate),2,2,6,6-tetramethyl-3,5-heptanedionate, and halogenatedacetylacetonoates such as 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate,1,1,1-trifluoro-2,4,pentanedionate; anions of acidic oxides of carbonsuch as carboxylates and halogenated carboxylates (e.g., acetates,2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and oxides ofnitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate,etc.), of aluminum (e.g., aluminates, etc.), of silicon (e.g., silicate,etc.), of phosphorous (e.g., phosphates, phosphites, phosphines, etc.)of sulfur (e.g., sulfates such as triflate, p-toluene sulfonate,sulfites, etc.); ylides; amides; imides; oxides; phosphides; sulfides;(C₆ to C₂₄) aryloxides, (C₁ to C₂₀) alkoxides, hydroxide, hydroxy (C₁ toC₂₀) alkyl; catechols; oxalate; chelating alkoxides and aryloxides.Palladium compounds can also contain complex anions such as PF⁻ ₆,AlF₃O₃SCF⁻ ₃, SbF⁻ ₆ and compounds represented by the formulae:

Al(R′″)⁻ ₄, B(X)⁻ ₄

[0114] wherein R′″ and X independently represent a halogen atom selectedfrom Cl, F, I, and Br, or a substituted or unsubstituted hydrocarbylgroup. Representative of hydrocarbyl are (C₁ to C₂₅) alkyl such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl octyl nonyl decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, and isomeric forms thereof; (C₂ toC₂₅) alkenyl such as vinyl allyl, crotyl, butenyl, pentenyl, hexenyl,octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, pentacosenyl, and isomeric forms thereof. (C₆ to C₂₅) arylsuch as phenyl tolyl, xylyl, naphthyl, and the like; (C₇ to C₂₅) aralkylsuch as benzyl, phenethyl, phenpropyl, phenbutyl, phenhexyl, napthoctyl,and the like; (C₃ to C₈) cycloalkyl such as cyclopropyl, cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl,2-norbornenyl, and the like. In addition to the above definitions Xrepresents the radical:

[0115] The term “substituted hydrocarbyl” means the hydrocarbyl group aspreviously defined wherein one or more hydrogen atoms have been replacedwith a halogen atom such as Cl, F, Br, and I (e.g., as in theperfluorophenyl radical); hydroxyl; amino; alkyl; nitro; mercapto, andthe like.

[0116] The Group VIII metal compounds can also contain cations such as,for example, organoammonium, organoarsonium, organophosphonium, andpyridinium compounds represented by the formulae:

[0117] wherein A represents nitrogen, arsenic, and phosphorous and theR²⁸ radical can be independently selected from hydrogen, branched orunbranched (C₁ to C₂₀) alkyl branched or unbranched (C₂ to C₂₀) alkenyl,and (C₅ to C₁₆) cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, and the like. R²⁹ and R³⁰ are independently selected fromhydrogen, branched and unbranched (C₁ to C₅₀) alkyl, linear and branched(C₂ to C₅₀) alkenyl and (C₅ to C₁₆) cycloalkyl groups as defined above;and n is 1 to 5, preferably n is 1, 2, or 3, most preferably n is 1. TheR³⁰ radicals preferably are attached to positions 3, 4, and 5 on thepyridine ring.

[0118] It should be noted that increasing the sum of the carbon atomscontained in the R²⁸ radicals confers better solubility of thetransition metal compound in organic media such as organic solvents andpolycyclic the monomer. Preferably, the R²⁸ radicals are selected from(C₁ to C₁₈) alkyl groups wherein the sum of carbon atoms for all R²⁸radicals is 15 to 72, preferably 25 to 48, more preferably 21 to 42. TheR²¹ radical is preferably selected from linear and branched (C₁ to C₅₀)alkyl more preferably (C₁₀ to C₄₀) alkyl. R³⁰ is preferably selectedfrom linear and branched (C₁ to C₄₀) alkyl, more preferably (C₂ to C₃₀)alkyl.

[0119] Specific examples of organoammonium cations includetridodecylammonium, methyltricaprylammonium, tris(tridecyl)ammonium andtrioctylammonium. Specific examples of organoarsonium andorganophosphonium cations include tridodecylarsonium and phosphonium,methyltricaprylarsonium and phosphonium, tris(tridecyl)arsonium andphosphonium, and trioctylarsonium and phosphonium. Specific pyridiniumcations include eicosyl-4-butylpentyl)pyridinium,docosyl-4-(13-pentacosyl)pyridinium, andeicosyl-4-(1-butylpentyl)pyridinium.

[0120] Suitable neutral ligands which can be bonded to the palladiumtransition metal are the olefins; the acetylenes; carbon monoxide;nitric oxide, nitrogen compounds such as ammonia, alkylisocyanide,alkylisocyanate, alkylisothiocyanate; pyridines and pyridine derivatives(e.g., 1,10-phenanthroline, 2,2′-dipyridyl),1,4-dialkyl-1,3-diazabutadienes, 1,4-diaryl-1,3-diazabutadienes andamines such as represented by the formulae:

[0121] wherein R³¹ is independently hydrocarbyl or substitutedhydrocarbyl as previously defined and n is 2 to 10. Ureas; nitriles suchas acetonitrile, benzonitrile and halogenated derivatives thereof;organic ethers such as dimethyl ether of diethylene glycol, dioxane,tetrahrydrofuran, furan diallyl ether, diethyl ether, cyclic ethers suchas diethylene glycol cyclic oligomers; organic sulfides such asthioethers (diethyl sulfide); arsines; stibines; phosphines such astriarylphosphines (e.g., triphenylphosphine), trialkylphosphines (e.g.,trimethyl, triethyl tripropyl, tripentacosyl, and halogenatedderivatives thereof), bis(diphenylphosphino)ethane,bis(diphenylphosphino)propane, bis(dimethylphosphino)propane,bis(diphenylphosphino)butane,(S-(−)2,2′-bis(diphenylphosphino)1,1′-binaphthyl,(R)-(+-2,2′-bis(diphenylphosphino-1,1′-binaphthyl, andbis(2-diphenylphosphinoethyl)phenylphosphine; phosphine oxides,phosphorus halides; phosphites represented by the formula:

P(OR³¹)₃

[0122] wherein R³¹ independently represents a hydrocarbyl or substitutedhydrocarbyl as previously defined; phosphorus oxyhalides; phosphonates;phosphonites, phosphinites, ketones; sulfoxides such as (C₁ to C₂₀)alkylsulfoxides; (C₆ to C₂₀) arylsulfoxides, (C₇ to C₄₀)alkarylsulfoxides, and the like. It should be recognized that theforegoing neutral ligands can be utilized as optional third componentsas will be described hereinbelow.

[0123] Examples of Group VIII transition metal compounds suitable as theGroup VIII metal ion source include: palladium ethylhexanoate, trans-PdCl₂(PPh₃)₂, palladium (II) bis(trifluoroacetate), palladium (II)bis(acetylacetonate), palladium (II) 2-ethylhexanoate,Pd(acetate)₂(PPh₃)₂, palladium (II) bromide, palladium (II) chloride,palladium (II) iodide, palladium (I) oxide,monoacetonitriletris(triphenylphosphine) palladium (II)tetrafluoroborate, tetrakis(acetonitrile) palladium (H)tetrafluoroborate, dichlorobis(acetonitrile) palladium (II),dichlorobis(triphenylphosphine) palladium (II),dichlorobis(benzonitrile) palladium (II), palladium acetylacetonate,palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide)dichloride, nickel acetylacetonates, nickel carboxylates, nickeldimethylglyoxime, nickel ethylhexanoate, NiCl₂(PPh₃)₂, NiCl₂(PPh₂CH₂)₂,(P(cyclohexyl)₃)H Ni(Ph₂P(C₆H₄)CO₂), (PPh₃) (C₆H₅)Ni(Ph₂ PCH═C(O)Ph),bis(2,2,6,6-tetramethyl-3,5-heptanedionate) nickel (II), nickel (II)hexafluoroacetylacetonate tetrahrydrate, nickel (II)trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonatetetrahrydrate, nickelocene, nickel (II) acetate, nickel bromide, nickelchloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide,nickel tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel,cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate,cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride,cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate,cobalt (II) tetrafluoroborate, iron napthenate, iron (II) chloride, iron(III) chloride, iron (II) bromide, iron (III) bromide, iron (II)acetate, iron (III) acetylacetonate, ferrocene, rutheniumtris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine)hydrido chloride, ruthenium trichloride, rutheniumtetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide)dichloride, rhodium chloride, rhodium tris(triphenylphosphine)trichloride.

[0124] The organoaluminum component of the multicomponent catalystsystem of the present invention is represented by the formula:

AlR³² _(3-x)Q_(x)

[0125] wherein R³² independently represents linear and branched (C₁ toC₂₀) alkyl, (C₆ to C₂₄) aryl, (C₇ to C₂₀) aralkyl, (C₃ to C₁₀)cycloalkyl; Q is a halide or pseudohalide selected from chlorine,fluorine, bromine, iodine, linear and branched (C₁ to C₂₀) alkoxy, (C₆to C₂₄) aryloxy; and x is 0 to 2.5, preferably 0 to 2.

[0126] Representative organoaluminum compounds include trialkylaluminumssuch as trimethylaluminum, triethylaluminum, tripropylaluminum,triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum,tri-3-methylbutylaluminum, tri-2-methylpentylaluminum,tri-3-methylpentylaluminum, tri-4-methylpentylaluminum,tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum,tris-2-norbornylaluminum, and the like; dialkylaluminum halides such asdimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminumchloride, diisobutylaluminum chloride, and the like; monoalkylaluminumdihalides such as methylaluminum dichloride, ethylaluminum dichloride,ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminumdichloride, butylaluminum dichloride, isobutylaluminum dichloride, andthe like; and alkylaluminum sesquihalides such as methylaluminumsesquichloride, ethylaluminum sesquichloride, propylaluminumsesquichloride, isobutylaluminum sesquichloride, and the like.

[0127] The dialkylaluminum hydride is selected from linear and branched(C₁ to C₁₀) dialkylaluminum hydride, with diisobutylaluminum hydridebeing a preferred dialkylaluminum hydride compound.

[0128] The dialkyl zinc compounds are selected from linear and branched(C₁ to C₁₀) dialkyl zinc compounds with diethyl zinc being preferred.The dialkyl magnesium compounds are selected from linear and branched(C₁ to C₁₀) dialkyl magnesium with dibutyl magnesium being the mostpreferred. The alkyl lithiums are selected from linear and branched (C₁to C₁₀) alkyl lithium compounds. Butyllithium is the preferred alkyllithium.

[0129] In the practice of the present invention, the catalytic systemobtained from the Group VIII metal ion source is utilized with one orboth of a component selected from the group of cocatalyst compounds, andthird component compounds.

[0130] Examples of third components are Lewis acids such as theBF₃-etherate, TiCl₄, SbF₅, tris(perfluorophenyl)boron, BCl₃,B(OCH₂CH₃)₃; strong Brønsted acids such as hexafluoroantimonic acid(HSbF₆), HPF₆ hydrate, trifluoroacetic acid (CF₃CO₂H), and FSO₃H.SbF₅,H₂C(SO₂CF₃)₂ CF₃SO₃H, and paratoluenesulfonic acid; halogenatedcompounds such as hexachloroacetone, hexafluoroacetone, 3-butenoicacid-2,2,3,4,4-pentachlorobutylester, hexafluoroglutaric acid,hexafluoroisopropanol and chloranil, i.e.,

[0131] electron donors such as phosphines and phosphites and olefinicelectron donors selected from (C₄ to C₁₂) aliphatic and (C₆ to C₁₂)cycloaliphatic diolefins, such as butadiene, cyclooctadiene, andnorbornadiene.

[0132] Acidity of strong Brønsted acids can be gauged by determiningtheir Hammett acidity function H₀. A definition of the Hammett acidityfunction is found in Advanced Inorganic Chemistry by F. A. Cotton and G.Wilkinson, Wiley-Interscience, 1988, p. 107.

[0133] As set forth above the neutral ligands can be employed asoptional third components with electron donating properties.

[0134] In one embodiment of the invention, the multicomponent catalystsystem can be prepared by a process which comprises mixing the catalystcomponents, i.e., the Group VIII metal compound, the cocatalystcompound, and third component (if employed), together in a hydrocarbonor halohydrocarbon solvent and then mixing the premixed catalyst systemin the reaction medium comprising at least one silyl functionalpolycyclic monomer. Alternatively, (assuming the optional thirdcomponent is utilized), any two of the catalyst system components can bepremixed in a hydrocarbon or halohydrocarbon solvent and then introducedinto the reaction medium. The remaining catalyst component can be addedto the reaction medium before or after the addition of the premixedcomponents.

[0135] In another embodiment, the multicomponent catalyst system can beprepared in situ by mixing together all of the catalyst components inthe reaction medium. The order of addition is not important.

[0136] In one embodiment of the multicomponent catalyst system of thepresent invention, a typical catalyst system comprises a Group VIIItransition metal salt, e.g., nickel ethylhexanoate, an organoaluminumcompound, e.g., triethylaluminum, and a mixture of third components,e.g., BF₃-etherate and hexafluoroantimonic acid (HSbF₆), in a preferredmolar ratio of Al/BF₃-etherate/Ni/acid of 10/9/1/0.5-2. The reactionscheme is written as follows:

[0137] 1. nickel ethylhexanoate+HSbF₆+9BF₃.etherate+10triethylaluminum→Active Catalyst

[0138] In another embodiment of the multicomponent catalyst system ofthe invention, the catalyst system comprises a nickel salt, e.g., nickelethylhexanoate, an organoaluminum compound, e.g., triethylaluminum, anda third component Lewis acid, e.g., tris(perfluorophenyl)boron as shownin the following scheme:

[0139] 2. nickelethylhexanoate+tris(perfluorophenyl)boron+triethylaluminum→ActiveCatalyst

[0140] In another embodiment of the multicomponent catalyst system ofthe invention the third component is a halogenated compound selectedfrom various halogenated activators. A typical catalyst system comprisesa Group VIII transition metal salt, an organoaluminum, and a thirdcomponent halogenated compound as shown below:

[0141] 3. nickel ethylhexanoate+triethylaluminum+chloranil→ActiveCatalyst

[0142] In still another embodiment of the multicomponent catalyst systemof this invention no cocatalyst is present. The catalyst systemcomprises a Group VIII metal salt (e.g. 3-allylnickelbromide dimer and aLewis acid (e.g. tris(perfluorophenyl)boron as shown below:

[0143] 4. η³-allylnickel chloride+tris(perfluorophenyl)boron→ActiveCatalyst

[0144] We have found that the choice of Group VIII metal in the metalcation complex of both the single and multicomponent catalyst systems ofthis invention influences the microstructure and physical properties ofthe polymers obtained. For example, we have observed that palladiumcatalysts typically afford norbornene units which are exclusively 2,3enchained and showing some degree of tacticity. The polymers catalyzedby the type 2 catalyst systems and the single component catalyst systemsof the formula E_(n)Ni(C₆F₅)₂ described above contain what we believe tobe exclusive 2,7-enchained repeating units. These polymers also containa perfluorophenyl group at at least one of the two terminal ends of thepolymer chain. In other words, a perfluorophenyl moiety can be locatedat one or both terminal ends of the polymer. In either case theperfluorophenyl group is covalently bonded to and pendant from aterminal polycyclic repeating unit of the polymer backbone.

[0145] Reactions utilizing the single and multicomponent catalysts ofthe present invention are carried out in an organic solvent which doesnot adversely interfere with the catalyst system and is a solvent forthe monomer. Examples of organic solvents are aliphatic (non-polar)hydrocarbons such as pentane, hexane, heptane, octane and decane;alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatichydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, toluene,and xylenes; halogenated (polar) hydrocarbons such as methylenechloride, chloroform, carbon tetrachloride, ethyl chloride,1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene,1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,1-chloro-2-methylpropane, and 1-chloropentane.

[0146] The choice of reaction solvent is made on the basis of a numberof factors including the choice of catalyst and whether it is desired torun the polymerization as a slurry or solution process. For most of thecatalysts described in this invention, the preferred solvents arechlorinated hydrocarbons such as methylene chloride and1,2-dichloroethane and aromatic hydrocarbons such as chlorobenzene andnitrobenzene, with simple hydrocarbons being less preferred due to theresulting lower conversion of the functional NB-type monomer(s).Surprisingly we have discovered that certain of the catalyst systems,most notably the multicomponent catalysts based on Group VIII metalcompounds and alkylaluminum halides, specifically, monoalkylaluminumdihalides, (e.g., ethylaluminum dichloride), and the type 2 catalystsreferred to above also give excellent results (and high monomerconversion) when run in simple hydrocarbons such as heptane,cyclohexane, and toluene.

[0147] The molar ratio of total monomer to Group VIII metal for thesingle and multicomponent catalysts can run from 20:1 to 100,000:1,preferably 50:1 to 20,000:1, and most preferably 100:1 to 10,000:1.

[0148] In the multicomponent catalyst systems, the cocatalyst metal(e.g., aluminum, zinc, magnesium, and lithium) to Group VIII metal molarratio ranges from less than or equal to 100:1, preferably less than orequal to 30:1, and most preferably less than or equal to 20:1.

[0149] The third component is employed in a molar ratio to Group VIIImetal ranging from 0.25:1 to 20:1. When acids are employed as thirdcomponents, the acid to Group VIII metal range is less than or equal to4:1, preferably less than or equal to 2:1.

[0150] The temperature at which the polymerization reactions of thepresent invention are carried out typically ranges from −100° C. to 120°C., preferably 60° C. to 90° C., and most preferably −10° C. to 80° C.

[0151] The optimum temperature for the present invention is dependent ona number of variables, primarily the choice of catalyst and the choiceof reaction diluent. Thus, for any given polymerization the optimumtemperature will be experimentally determined taking these variablesinto account.

[0152] In the course of developing these catalyst and polymer systems wehave observed that the palladium-carbon bond which links the palladiumcatalysts to the growing polymer chain is particularly stable. This is amajor benefit in polymerizing polycyclic monomers bearing acid labilegroups, esters and carboxylic acid functionalities since the palladiumcatalysts are extremely tolerant to such functionalities. However, thisstability also makes it very difficult to remove the palladium catalystresidues from the resulting polymer. During the development of these newcompositions, we discovered that the palladium-carbon bond can beconveniently-cleaved (resulting in precipitation of palladium metalwhich can be removed by filtration or centrifugation) using carbonmonoxide, preferably in the presence of a protic solvent such as analcohol, moisture, or a carboxylic acid.

[0153] The polymers obtained by the process of the present invention areproduced in a molecular weight (M.) range from about 1,000 to about1,000,000, preferably from about 2,000 to about 700,000, and morepreferably from about 5,000 to about 500,000 and most preferably fromabout 10,000 to about 50,000.

[0154] Molecular weight can be controlled by changing the catalyst tomonomer ratio, i.e., by changing the initiator to monomer ratio. Lowermolecular weight polymers and oligomers may also be formed in the rangefrom about 500 to about 500,000 by carrying out the polymerization inthe presence of a chain transfer agent. Macromonomers or oligomerscomprising from 4 to 50 repeating units can be prepared in the presenceof a CTA (Chain Transfer Agent) selected from a compound having aterminal olefinic double bond between adjacent carbon atoms, wherein atleast one of the adjacent carbon atoms has two hydrogen atoms attachedthereto. The CTA is exclusive of styrenes (non-styrenes), vinyl ethers(non-vinyl ether) and conjugated dienes. By non-styrenic, non-vinylether is meant that compounds having the following structures areexcluded from the chain transfer agents of this invention:

[0155] wherein A is an aromatic substituent and R is hydrocarbyl.

[0156] The preferred CTA compounds of this invention are represented bythe following formula:

[0157] wherein R′ and R″ independently represent hydrogen, branched orunbranched (C₁ to C₄₀) alkyl, branched or unbranched (C₂ to C₄₀)alkenyl, halogen, or the group.

[0158] Of the above chain transfer agents the α-olefins having 2 to 10carbon atoms are preferred, e.g., ethylene, propylene,4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene, and1,6-octadiene, or isobutylene.

[0159] While the optimum conditions for any given result should beexperimentally determined by a skilled artisan taking into the accountall of the above factors there are a number of general guidelines whichcan be conveniently utilized where appropriate. We have learned that, ingeneral, α-olefins (e.g., ethylene, propylene, 1-hexene, 1-decene,4-methyl-1-pentene) are the most effective chain transfer agents with1,1-disubstituted olefins (e.g., isobutylene) being less efficient. Inother words, all other things being equal, the concentration ofisobutylene required to achieve a given molecular weight will be muchhigher than if ethylene were chosen. Styrenic olefins, conjugateddienes, and vinyl ethers are not effective as chain transfer agents dueto their propensity to polymerize with the catalysts described herein.

[0160] The CTA can be employed in an amount ranging from about 0.10 mole% to over 50 mole % relative to the moles of total NB-type monomer.Preferably, the CTA is employed in the range of 0.10 to 10 mole %, andmore preferably from 0.1 to 5.0 mole %. As discussed above, depending oncatalyst type and sensitivities, CTA efficiencies and desired end group,the concentration of CTA can be in excess of 50 mole % (based on totalNB-functional monomer present), e.g., 60 to 80 mole %. Higherconcentrations of CTA (e.g., greater than 100 mole %) may be necessaryto achieve the low molecular weight embodiments of this invention suchas in oligomer and macromonomer applications. It is important andsurprising to note that even such high concentrations the CTA's (withthe exception of isobutylene) do not copolymerize into the polymerbackbone but rather insert as terminal end-groups on each polymer chain.Besides chain transfer, the process of the present invention affords away by which a terminal α-olefinic end group can be placed at the end ofa polymer chain.

[0161] Polymers of the present invention that are prepared in thepresence of the instant CTA's have molecular weights (M_(n)) rangingfrom about 1,000 to about 500,000, preferably from about 2,000 to about300,000, and most preferably from about 5,000 to about 200,000.

[0162] The photoresist compositions of the present invention comprisethe disclosed polycyclic compositions, a solvent, and an photosensitiveacid generator (photoinitiator). Optionally, a dissolution inhibitor canbe added in an amount of up to about 20 weight % of the composition. Asuitable dissolution inhibitor is t-butyl cholate (J. V. Crivello etal., Chemically Amplified Electron-Beam Photoresists, Chem. Mater.,1996, 8, 376-381).

[0163] Upon exposure to radiation, the radiation sensitive acidgenerator generates a strong acid. Suitable photoinitiators includetriflates (e.g., triphenylsulfonium triflate), pyrogallol (e.g.,trimesylate of pyrogallol); onium salts such as triarylsulfonium anddiaryliodium hexafluoroantimonates, hexafluoroarsenates,trifluoromethanesulfonates; esters of hydroxyimides,α,α′-bis-sulfonyl-diazomethanes, sulfonate esters of nitro-substitutedbenzyl alcohols and napthoquinone-4-diazides. Other suitable photoacidinitiators are disclosed in Reichmanis et al., Chem. Mater. 3, 395,(1991). Compositions containing triarylsulfonium or diaryliodonium saltsare preferred because of their sensitivity to deep UV light (193 to 300nm) and give very high resolution images. Most preferred are theunsubstituted and symmetrically or unsymmetrically substituteddiaryliodium or triarylsulfonium salts. The photoacid initiatorcomponent comprises about 1 to 100 w/w % to polymer. The preferredconcentration range is 5 to 50 w/w %.

[0164] The photoresist compositions of the present invention optionallycontain a sensitizer capable of sensitizing the photoacid initiator tolonger wave lengths ranging from mid UV to visible light. Depending onthe intended application, such sensitizers include polycyclic aromaticssuch as pyrene and perlene. The sensitization of photoacid initiators iswell-known and is described in U.S. Pat. Nos. 4,250,053; 4,371,605; and4,491,628 which are all incorporated herein by reference. The inventionis not limited to a specific class of sensitizer or photoacid initiator.

[0165] The present invention also relates to a process for generating apositive tone resist image on a substrate comprising the steps of: (a)coating a substrate with a film comprising the positive tone resistcomposition of the present invention; (b) imagewise exposing the film toradiation; and (c) developing the image.

[0166] The first step involves coating the substrate with a filmcomprising the positive tone resist composition dissolved in a suitablesolvent. Suitable substrates are comprised of silicon, ceramics, polymeror the like. Suitable solvents include propylene glycol methyl etheracetate (PGMEA) cyclohexanone, butyrolactate, ethyl lactate, and thelike. The film can be coated on the substrate using art known techniquessuch as spin or spray coating, or doctor blading. Preferably, before thefilm has been exposed to radiation, the film is heated to an elevatedtemperature of about 90° C. to 150° C. for a short period of time ofabout 1 min. In the second step of the process, the film is imagewiseexposed to radiation suitably electron beam or electromagneticpreferably electromagnetic radiation such as ultraviolet or x-ray,preferably ultraviolet radiation suitably at a wave length of about 193to 514 nm preferably about 193 nm to 248 nm. Suitable radiation sourcesinclude mercury, mercury/xenon, and xenon lamps, x-ray or e-beam. Theradiation is absorbed by the radiation-sensitive acid generator toproduce free acid in the exposed area. The free acid catalyzes thecleavage of the acid labile pendant group of the copolymer whichconverts the copolymer from dissolution inhibitor to dissolutionenhancer thereby increasing the solubility of the exposed resistcomposition in an aqueous base. Surprisingly, the exposed resistcomposition is readily soluble in aqueous base. This solubility issurprising and unexpected in light of the complex nature of thecycloaliphatic backbone and the high molecular weight of the norbornenemonomer units bearing the carboxylic acid functionality. Preferably,after the film has been exposed to radiation, the film is again heatedto an elevated temperature of about 90° C. to 150° C. for a short periodof time of about 1 minute.

[0167] The third step involves development of the positive tone imagewith a suitable solvent. Suitable solvents include aqueous basepreferably an aqueous base without metal ions such as tetramethylammonium hydroxide or choline. The composition of the present inventionprovides positive images with high contrast and straight walls.Uniquely, the dissolution property of the composition of the presentinvention can be varied by simply varying the composition of thecopolymer.

[0168] The present invention also relates to an integrated circuitassembly such as an integrated circuit chip, multichip module, orcircuit board made by the process of the present invention. Theintegrated circuit assembly comprises a circuit formed on a substrate bythe steps of: (a) coating a substrate with a film comprising thepositive tone resist composition of the present invention; (b) imagewiseexposing the film to radiation; (c) developing the image to expose thesubstrate; and (d) forming the circuit in the developed film on thesubstrate by art known techniques.

[0169] After the substrate has been exposed, circuit patterns can beformed in the exposed areas by coating the substrate with a conductivematerial such as conductive metals by art known techniques such asevaporation, sputtering, plating, chemical vapor deposition, or laserinduced deposition. The surface of the film can be milled to remove anyexcess conductive material. Dielectric materials may also be depositedby similar means during the process of making circuits. Inorganic ionssuch as boron, phosphorous, or arsenic can be implanted in the substratein the process for making p or n doped circuit transistors. Other meansfor forming circuits are well known to those skilled in the art.

[0170] The following examples are detailed descriptions of methods ofpreparation and use of certain compositions of the present invention.The detailed preparations fall within the scope of and serve toexemplify, the more generally described methods of preparation set forthabove. The examples are presented for illustrative purposes only, andare not intended as a restriction on the scope of the invention.

[0171] As discussed above, photoresists are used to create and replicatea pattern from a photomask to a substrate. The efficacy of this transferis determined by the wave length of the imaging radiation, thesensitivity of the photoresist and the ability of the photoresist towithstand the etch conditions which pattern the substrate in the exposedregions. Photoresists are most often used in a consumable fashion, wherethe photoresist is etched in the non-exposed regions (for a positivetone photoresist) and the substrate is etched in the exposed regions.Because the photoresist is organic and the substrate is typicallyinorganic, the photoresist has an inherently higher etch rate in thereactive ion etch (RIE) process, which necessitates that the photoresistneeds to be thicker than the substrate material. The lower the etch rateof the photoresist matter, the thinner the photoresist layer has to be.Consequently, higher resolution can be obtained. Therefore, the lowerthe RIE rate of the photoresist, the more attractive it is from aprocess point of view. The etch rate is primarily determined by thepolymer backbone, as shown below for the chlorine plasma etch processwhich is a RE technique typically employed in semiconductor processing.

[0172] As used in the examples and throughout the specification theratio of monomer to catalyst is based on a mole to mole basis.Normalized No. Polymer RIE Rate (μm/min) 1 Novolac resist 1.0  2polyhydroxystyrene resist 0.98 3 248 nm (Deep UV) 1.14 (acrylateterpolymer/novolac blend, U.S. Pat. No. 5,372,912) 4 193 nm(polyacrylate terpolymer, 1.96 Allen et al., Proceedings SPIE, 2438(1),474 (1995)) 5 homopolynorbornene 0.83

[0173] Polymers 1 and 2 are primarily aromatic, whereas polymer 3 wascopolymerized with a small amount of acrylate which increased its etchrate. Polymer 4 is completely based on acrylates to allow transparencyat 193 nm (aromatic rings render the material opaque in this region,hence there are no viable resist candidates at 193 nm based on thetraditional novolacs or p-hydroxystyrene). The etch rate almost doubledfor this polymer. Polymer 5 had an etch rate even lower than thestandard photoresist materials (1 & 2) in addition to providingtransparency at 193 nm. Therefore, the backbone of polymer 5 (anaddition cyclic olefin) prepared by a nickel multicomponent catalyst ofthis invention is an improvement over all previous attempts in theliterature to provide a resist which functions at 193 nm with RIEcharacteristics comparable to commercial materials exposed at longerwave lengths. In fact, the addition cyclic olefin polymer may offeradvantages in terms of etch resistance at longer wave lengths as well.It is in the literature (H. Gokan, S. Esho, and Y. Ohnishi, J.Electrochem. Soc. 130(1), 143 (1983)) that higher C/H ratios decreasesthe etch rate of polymeric materials. Based on this assumption, the etchrate of polymer 5 should be between the aromatic based systems and theacrylate systems. It is surprising that. the addition cyclic olefinexhibits etch resistance superior to even the aromatic systems.

EXAMPLE 1

[0174] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded the t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (2.0 g, 10.3 mmol, exo,endo 44/56). To thisstirred monomer at ambient temperature was added a catalyst solutionprepared by adding η³-allylpalladium chloride dimer (38 mg, 103 μmol) inchlorobenzene (5 ml) to silver hexafluoroantimonate (99 mg, 290 μmol) inchlorobenzene (5 ml) for 30 minutes and then filtering through amicropore filter (to remove the precipitated silver chloride). Thereaction was allowed to run for 36 hours at which time the mixture hadgelled to form a clear yellow gel. Upon adding the gel to excessmethanol the polymer precipitated as a white powder. The polymer waswashed with excess methanol and dried. The yield of polymer was 1.5 g(75%). The presence of the ester-bearing monomer in the polymer wasverified by infra-red analysis which showed strong bands at 1728 cm⁻¹(C═O stretch), 1251 cm⁻ (C—O—C stretch) and 1369 and 1392 cm⁻¹(characteristic of t-butyl groups) and the absence of unconvertedmonomer (proton NMR). The polymer was found to have a molecular weight(M_(w)) of 22,500. Thermogravimetric analysis (TGA) under nitrogen(heating rate 10° C. per minute) showed the polymer to be thermallystable to about 210° C. and then to exhibit approximately 28% weightloss by 260° C. (indicating clean loss of the t-butyl groups asisobutene to afford the homopolymer of 5-norbornene-carboxylic acid) andthen degradation of the polymer (90% total weight loss) at around 400°C.

EXAMPLE 2

[0175] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded norbornene (0.8 g, 8.6 mmol), 1,2-dichloroethane (8 ml) and thet-butylester of 5-norbornene-carboxylic acid (carbo-t-butoxynorbornene)(0.2 g, 1 mmol, exo,endo 44/56). To this stirred solution at ambienttemperature was added nickel ethylhexanoate (3 μmol),trisperfluorophenylboron (23 μmol) and triethylaluminum (27 μmol). Thereensued an immediate reaction with white polymer precipitating fromsolution within less than 10 seconds. The reaction was allowed to runfor 60 minutes before the reactor contents were dissolved in cyclohexaneand poured into an excess of methanol. The polymer was washed withexcess methanol and dried overnight in a vacuum oven at 80° C. The yieldof copolymer was 0.9 g (90%). The molecular weight of the copolymer wasdetermined using GPC methods and found to be 535,000 (M_(w)) with apolydispersity of 4.7.

EXAMPLE 3

[0176] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded the t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (2.2 g, 11.3 mmol exo,endo 44/56). To thisstirred monomer at ambient temperature was added a catalyst solutionprepared by adding η³-allylpalladium chloride dimer (29 mg, 74 μmol) indichloroethane (6 ml) to silver tetrafluoroborate (61 mg, 311 μmol) indichloroethane (6 ml) for 30 minutes and then filtering through amicropore filter (to remove the precipitated silver chloride). Thereaction was allowed to run for 36 hours at which time the mixture hadgelled to form a clear yellow gel. Upon adding the gel to excessmethanol the polymer precipitated as a white powder. The polymer waswashed with excess methanol and dried. The yield of polymer was 1.4 g(64%). The presence of the ester-bearing monomer in the polymer wasverified by infra-red analysis which showed strong bands at 1728 cm⁻¹(C═O stretch), 1251 cm⁻¹ (C—O—C stretch) and 1369 and 1392 cm⁻¹(characteristic of t-butyl groups) and the absence of unconvertedmonomer or carboxylic acid functionality (proton NMR and IR). Thepolymer was found to have a molecular weight (M_(w)) of 54,100.Thermogravimetric analysis (TGA) under nitrogen (heating rate 10° C. perminute) showed the polymer to be thermally stable to about 210° C. andthen to exhibit approximately 29% weight loss by 250° C. (indicatingclean loss of the t-butyl groups as isobutene to afford the homopolymerof 5-norbornene-carboxylic acid) and then degradation of the polymer(80% total weight loss) at around 400° C.

EXAMPLE 4

[0177] To a 100 ml glass vial equipped with a Teflon® coated stir barwas added norbornene (1.16 g, 12.3 mmol), 1,2-dichloroethane (50 ml) andthe t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (0.6 g, 3.1 mmnol exo,endo 44/56). To thisstirred solution at ambient temperature was added palladiumbis(2,2,6,6-tetramethyl-3,5-pentanedionate (31 μmol) andtrisperfluorophenylboron (279 μmol). The reaction was allowed to run for16 hours before the reactor contents were poured into an excess ofmethanol. The polymer was washed with excess methanol and driedovernight in a vacuum oven at 80° C. The yield of copolymer was 0.54 g(31%).

EXAMPLE 5

[0178] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded the t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (4.4 g, 22.7 mmol, exo,endo 44/56). To thisstirred monomer at ambient temperature was added a catalyst solutionprepared by adding η³-allylpalladium chloride dimer (41.5 mg, 113 μmol)in dichloroethane (7 ml) to silver tetafluoroborate (42 mg, 215 μmol) indichloroethane (7 ml) for 30 minutes and then filtering through amicropore filter (to remove the precipitated silver chloride). Thereaction mixture was then warmed in an oil bath to 75° C. After 90minutes it was observed that the mixture had solidified to a greypolymeric mass. The mass was dissolved in acetone to afford a darkcolored solution. Gaseous carbon monoxide was bubbled through thesolution for 30 minutes resulting in copious amounts of a finely dividedblack precipitate (metallic palladium and possibly other catalystresidues). The precipitate was removed via centrifugation, and thisprocess was repeated two more times. Finally the resulting colorlesssolution was filtered through a 45 micron microdisc and the polymer wasprecipitated by adding the acetone solution to an excess of hexane. Thewhite polymer was separated using a centrifuge and then dried overnightto afford the copolymer as a white powder (2.21 g, 50%).Thermogravimetric analysis (TGA) under nitrogen (heating rate 10° C. perminute) showed the polymer to be thermally stable to about 210° C. andthen to exhibit approximately 28% weight loss by 260° C. (indicatingclean loss of the t-butyl groups as isobutene to afford the homopolymerof 5-norbornene-carboxylic acid) and then degradation of the polymer(90% total weight loss) at around 400° C. The molecular weight wasobserved to be Mn=3,300 g/mole and Mw=6,900 g/mole (GPC in THF,polystyrene standards).

EXAMPLE 6

[0179] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded the pure exo isomer of the t-butylester of 5-norbornene-carboxylicacid (carbo-t-butoxynorbornene) (0.6 g). To this stirred monomer atambient temperature was added a catalyst solution prepared by addingη³-allyl-palladium chloride dimer (30 mg) in dichloroethane (10 ml) tosilver hexafluoroantimonate (50 mg) in dichloroethane (20 ml) for 30minutes and then filtering through a micropore filter (to remove theprecipitated silver chloride). The reaction was allowed to run for 15hours at which time the mixture was added to excess methanol causing thepolymer to precipitate as a white powder. The polymer was washed withexcess methanol and dried. The yield of polymer was 0.5 g (85%). Thepolymer was found to have a molecular weight (Me) of 46,900, and apolydispersity of 2.4.

EXAMPLE 7

[0180] To a 100 ml glass vial equipped with a Teflon® coated stir barwas added norbornene (4.01 g, 42.6 mmol), 1,2-dichloroethane (50 ml) andthe t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (2 g, 10.3 mmol, exo,endo mixture). To thisstirred solution at ambient temperature was added a catalyst solutionprepared by reacting η³-allylpalladium chloride dimer (10 mg, 27.3 μmol)with silver hexafluoroantimonate (19.6 mg, 57 μmol) in1,2-dichloroethane (3 ml) for 30 minutes and then filtering through amicropore filter. The reaction was allowed to run for 20 hours beforethe reactor contents were poured into an excess of methanol. The polymerwas washed with excess methanol and dried. The yield of copolymer was4.15 g. The molecular weight of the copolymer was determined using GPCmethods and found to be 618,000 (M_(w)) with a polydispersity of 7.1.

EXAMPLE 8

[0181] To a 100 ml glass vial equipped with a Teflon® coated stir barwas added norbornene (3.75 g, 39.8 mmol), 1,2-dichloroethane (50 ml) andthe t-butylester of 5-norbornene-carboxylic acid(carbo-t-butoxynorbornene) (2 g, 10.3 mmol, exo,endo mixture). To thisstirred solution at ambient temperature was added palladiumethylhexanoate (12 μmol, tris(perfluorophenylboron (108 μmol) andtriethylaluminum (120 μmol). The reaction was allowed to run for 72hours before the reactor contents were poured into an excess ofmethanol. The polymer was washed with excess methanol and dried,redissolved in chlorobenzene and reprecipitated with an excess ofmethanol, filtered, and washed with methanol before finally drying in avacuum oven overnight at 80° C. The yield of copolymer was 1.66 g. Themolecular weight of the copolymer was determined using GPC methods andfound to be 194,000 (M_(w)) with a polydispersity of 2.3. The presenceof the ester-bearing monomer in the copolymer was verified by infra-redanalysis which showed bands at 1730 cm⁻¹ (C═O stretch) and 1154 cm⁻¹(C—O—C stretch) and the absence of unconverted monomer (proton NMR).

EXAMPLE 9

[0182] To a 100 ml glass vial equipped with a Teflon® coated stir barwas added 1,2-dichloroethane (25 ml) and the t-butylester of5-norbornene-carboxylic acid (carbo-t-butoxynorbornene) (10 g, 51.5mmol, exo,endo mixture). To this stirred solution at ambient temperaturewas added a catalyst solution prepared by reacting η³-allylpalladiumchloride dimer (82 mg, 223 μmol) with silver hexafluoroantimonate (200mg, 581 μmol) in 1,2-dichloroethane (10 ml) for 30 minutes and thenfiltering through a micropore filter. The reaction was allowed to runfor 48 hours before the reactor contents were poured into an excess ofmethanol. The polymer was washed with excess methanol and dried. Theyield of homopolymer was 4.5 g.

EXAMPLE 10

[0183] To a 100 ml glass vial equipped with a Teflon® coated stir barwas added 1,2-dichloroethane (50 ml), the t-butylester of5-norbornene-carboxylic acid (carbo-t-butoxynorbornene) (5 g, 25.8 mmolexo,endo mixture), norbornene (0.82 g, 8.7 mmol) and5-triethoxysilylnorbornene (0.47 g, 1.8 mmol). To this stirred solutionat ambient temperature was added a catalyst solution prepared byreacting η³-allylpalladium chloride dimer (47.2 mg, 128 μmol) withsilver tetrafluoroborate (138 mg, 700 μmol) in 1,2-dichloroethane (10ml) for 30 minutes and then filtering through a micropore filter. Thereaction was allowed to run for 48 hours before the reactor contentswere poured into an excess of methanol. The polymer was washed withexcess methanol and dried. The yield of terpolymer was 5.3 g. Themolecular weight of the copolymer was determined using GPC methods andfound to be 39,900 (M_(w)) with a polydispersity of 3.2.

EXAMPLE 11

[0184] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded 7.25 g (37.5 mmole) of the t-butylester of norbornene, 1.9 g (12.5mmole) of methylester of norbornene, 50 ml of freshly distilleddichloroethane and the solution was degassed under argon atmosphere. A10 ml glass vial equipped with a Teflon® coated stir bar was chargedwith 0.0365 g (0.1 mmol) of η³-allylpalladium chloride dimer (toultimately give a monomer to catalyst ratio of 500/1) and 2 ml ofdichloroethane. Into another 10 ml glass vial was charged with 0.0344 g(0.1 mmol) of silver hexafluoroantimonate and 2 ml of dichloroethane.The catalyst solution was prepared by mixing the allylpalladium chloridedimer solution with silver hexafluoroantimonate solution inside the drybox. Immediate precipitation of the silver chloride salt was observed,which was filtered, to obtain a clear yellow solution. The active yellowcatalyst solution was added to the monomer solution via a syringe andthe reaction mixture was allowed to stir for 20 hours at 60° C. Noappreciable increase in viscosity was observed, but solids hadprecipitated in the solution, the solution was cooled, concentrated in arotovap, and precipitated into hexane to obtain a white polymer.Yield=2.3 g, 26%. The polymer was dried in vacuum at room temperatureand analyzed using GPC for molecular weight. GPC was obtained in THFusing polystyrene standards. The molecular weight was observed to beM_(n)=1950 g/mole and M_(w)=3150 g/mole. ¹H NMR indicated the presenceof both methyl and t-butyl ester of norbornene and also a small amountof the t-butyl hydrolyzed product, the acid.

EXAMPLE 12

[0185] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded 2.42 g (12.5 mmole) of t-butylester of norbornene, 5.7 g (37.5mmole) of methylester of norbornene, 50 ml of freshly distilleddichloroethane, and the solution was degassed under argon atmosphere. A10 ml glass vial equipped with a Teflon® coated stir bar was chargedwith 0.0365 g (0.1 mmol) of allylpalladium chloride dimer in a monomerto catalyst ratio of 500/1 and 2 ml of dichloroethane. Into another 10ml glass vial was charged with 0.0344 g (0.1 mmol) of silver hexafluoroantimunate and 2 ml of dichloroethane. The catalyst solution wasprepared by mixing the allylpalladium chloride dimer solution withsilver hexafluoroantimonate solution inside the dry box. Immediateprecipitation of the silver chloride salt was observed, which wasfiltered, to obtain a clear yellow solution. The active yellow catalystsolution was added to the monomer solution via a syringe and thereaction mixture was allowed to stir for 20 hours at 60° C. Noappreciable increase in viscosity was observed, but solids had ppt inthe solution, the solution was cooled, concentrated in a rotovap, andprecipitated into hexane to obtain a white polymer. Yield=2.05 g, 25%.The polymer was dried in vacuum at room temperature and analyzed usingGPC for molecular weight. GPC was obtained in THF using Polystyrenestandards. The molecular weight was observed to be M_(n)=1440 g/mole andM_(w)=2000 g/mole. ¹H NMR indicated the presence of both methyl andt-butyl ester of norbornene and also a small amount of the t-butylhydrolyzed product, the acid.

EXAMPLE 13

[0186] To a 25 ml glass vial equipped with a Teflon® coated stir bar wasadded 2 g (7.94 mmole) of pure of bicyclo[2.2.1]hept-5-eneexo,-2-t-butyl, exo-3-methyl ester of dicarboxylic acid followed by 15ml of freshly distilled methylene chloride and 10 ml of methanol; andthe solution was degassed under argon atmosphere. A 10 ml glass vialequipped with a Teflon® coated stir bar was charged with 0.00588 g(0.0158 mmol) of ³-allylpalladium chloride dimer in a monomer tocatalyst ratio of 500/1 and 2 ml of methylene chloride. Into another 10ml glass vial was charged with 0.0108 g (0.0312 mmol) of silverhexafluoroantimonate and 2 ml of methylene chloride. The catalystsolution was prepared by mixing the η³-allylpalladium chloride dimersolution with silver hexafluoroantimonate solution inside the dry box.Immediate precipitation of the silver chloride salt was observed, whichwas filtered, to obtain a clear yellow solution. The active yellowcatalyst solution was added to the monomer solution via a syringe at 50°C. and the reaction mixture was allowed to stir for 16 hours at roomtemperature. No appreciable increase in viscosity was observed and thesolution was filtered through a 0.5μ filter, concentrated using arotovap. The thick solution was dissolved in methanol and ppt intomethanol/water mixture to obtain a white solid yield (65%). Themolecular weight was observed to be Mn=10,250 g/mole and Mw=19,700g/mole (GPC in the THF, polystyrene standards). ¹H NMR indicates thepresence of both methyl and t-butyl ester of norbornene.

EXAMPLE 14

[0187] To a 25 ml glass vial equipped with a Teflon® coated stir bar wasadded 3.06 g (12.8 mmole) of pure ofbicyclo[2.2.1]hept-5-ene-exo,exo-2,3-dicarboxylic acid diethyl ester,2.5 g (12.8 mmole) of t-butylester of norbornene, followed by 15 ml offreshly distilled methylene chloride and 10 ml of methanol, and thesolution was degassed under argon atmosphere. A 10 ml glass vialequipped with a Teflon® coated stir bar was charged with 0.0188 g (0.052mmol) of allylpalladium chloride dimer (to give a monomer to catalystratio of 500/1) and 2 ml of methylene chloride. Into another 10 ml glassvial was charged with 0.0357 g (0.104 mmol) of silverhexafluoroantimonate and 2 ml of methylene chloride. The catalystsolution was prepared by mixing the allylpalladium chloride dimersolution with silver hexafluoroantimonate solution inside the dry box.Immediate precipitation of the silver chloride salt was observed, whichwas filtered, to obtain a clear yellow solution. The active yellowcatalyst solution was added to the monomer solution via a syringe at 50°C. and the reaction mixture was allowed to stir for 16 hours at roomtemperature. No appreciable increase in viscosity was observed and thesolution was filtered through a 0.51μ filter, concentrated using arotovap. The resulting viscous solution was dissolved in methanol andprecipitated into methanol/water mixture to obtain a white solid yield(23%). The molecular weight was observed to be Mn=15,700 g/mole andMw=32,100 g/mole (GPC in THF, polystyrene standards). ¹H NMR indicatesthe presence of both methyl and t-butyl ester of norbornene.Thermogravimetric analysis (TGA) under nitrogen (heating rate 10°C./min.) showed the polymer to be thermally stable to about 155° C. andthen to exhibit approximately 20 wt. % loss by 290° C. (indicating cleanloss of the t-butyl groups as isobutylene to afford the homopolymer of5-norbornene-carboxylic acid) and then degradation of the polymer ataround 450° C.

EXAMPLE 15

[0188] Synthesis of bicyclo[2.2.1]hept-5-ene-exo, exo-2,3-dicarboxylicAcid Diethyl Ester:

[0189] The exo, exo diethyl ester of norbornene was synthesized fromexo-5-norbornene-2,3-dicarboxylic acid. The exo isomer was prepared bythermal conversion of the endo-5-norbornene-2,3-dicarboxylic anhydrideat 190° C. followed by recrystallization from toluene several times asin reference 1 to obtain pure exo-5-norbornene-2,3-dicarboxylicanhydride. Part of the exo-anhydride was hydrolyzed in boiling water andthe solution was cooled to obtain pure diacid in almost quantitativeyield. The diacid was converted to the diethyl ester usingtriethyloxonium salts as shown below:

[0190] A 250 ml, three necked, round bottomed flask with a magneticstirring bar was charged with 16.0 g (0.0824 mole) of pure exonorbornene dicarboxylic acid and 35 g (0.1846 mole) of triethyloxoniumtetrafluoroborate. The flask was stoppered, and to this 300 ml ofdichloromethane was added via a cannula under argon atmosphere. Therubber stopper was replaced with a condenser under argon atmosphere andthe other neck was fitted with an additional funnel. To the additionalfunnel was added 35 ml of ethyldiisopropyl amine and it was allowed todrip into the reaction vessel slowly. A small exotherm was observed andthe solution was allowed to reflux lightly. After the complete additionof the amine, the solution was allowed to stand at room temperature for15 hours. Work-up is initiated by extracting the reaction mixture withthree 50 ml portions of HCl solution, followed by three 50 mlextractions with sodium bicarbonate and finally washed two times withwater. The organic solution was dried over magnesium sulfate, treatedwith carbon black, filtered, concentrated on a rotary evaporator.Purification of the residue by distillation at 110° C. provides 15 g(75%) of pure exo-diethyl ester of norbornene as a colorless, viscous,fruity smelling liquid.

[0191]¹H NMR (CDCl₃): d=1.22 (3H; t, CH₃), d=1.47 (1H), d=2.15 (1H),d=2.58 (2H; s, CHCOO), d=3.07 (2H; s,bridge head), d=4.10 (2H; m, CH),d=6.19 (2H; s, C═C), FI-MS (DIP)=M⁺ (238).

EXAMPLE 16

[0192] Synthesis of bicyclo[2.2.1]hept-5-ene-exo-2-t-butylester,exo-3-carboxylic Acid:

[0193] To a 50 ml single necked round bottom flask equipped with aTeflon® coated stir bar was added 1.5 g (9.15 mmole) of pureexo-Nadicanhydride, 10 ml of freshly distilled methylenechloride, 20 mLof t-butanol (0.209 moles). To the solution was added 7.5 g (0.061moles) of dimethylamino pyridine and the solution was refluxed at 75° C.for 8 hours. Initially the anhydride was not soluble, but over theperiod of time the solids had dissolved and the solution had turnedbrown. The reaction was cooled, concentrated in a rotovap to removemethylene chloride and the thick solution was added slowly intoacidified water (HCl). The solid that precipitated out was filtered,washed with water and further dissolved in ether treated with MgSO₄,followed by carbon black and the solution was filtered over Celite. Theether was removed over a rotovap to obtain a white solid (yield 8.5 g60/).

[0194]¹H NMR(CDCl₃): d=1.47 (9H; s, t-butyl), d=1.60 (1H), d=2.15 (1H),d=2.58 (2H; m, CHCOO), d=3.07 (2H; s,bridge head),d=6.19 (2H; s, C═C),d=10.31 (1H; broad, COOH).

EXAMPLE 17

[0195] Synthesis of bicyclo[2.2.1]hept-5-ene-exo-2-t-butyl,exo-3-methylEster of Dicarboxylic Acid:

[0196] A 100 ml, three necked, round bottomed flask with a magneticstirring bar was charged with 9.7 g (0.0408 mole) of pure exo t-butylhalf ester of norbornene dicarboxylic acid and 6.05 g (0.0408 mole) oftrimethyloxonium tetrafluoroborate. The flask was stoppered, and to this100 ml of dichloromethane was added via a cannula under argonatmosphere. The rubber stopper was replaced with a condenser under argonatmosphere and the other neck was fitted with an additional funnel. Tothe additional funnel was added 7.3 ml of ethyldiisopropyl amine and itwas allowed to drip into the reaction vessel slowly. Small exotherm wasobserved and the solution was observed to reflux lightly. After thecomplete addition of the amine, the solution was allowed to stand atroom temperature for 15 hours. Work-up is initiated by extracting thereaction mixture with three 50 ml portion of HCl solution, followed bythree 50 ml extractions with sodium bicarbonate and finally washed twotimes with water. The organic solution was dried over magnesium sulfate,treated with carbon black, filtered, concentrated on a rotaryevaporator. A colorless liquid was obtained which started tocrystallize. The solid was washed with cold pentane and the pentanesolution was concentrated in a rotovap to obtain a colorless liquidwhich on cooling crystallized. Yield 5.1 g.

[0197]¹H NMR (CDCl₃): d=1.45 (9H; s, t-butyl), d=1.47 (1H), d 2.15 (1H),d=2.54 (2H; m, CHCOO), d=3.07 (2H; s,bridge head), d=3.65 (3H; s, CH₃),d=6.19 (2H; s, C═C)

EXAMPLE 18

[0198] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded 5-norbornene-carboxylic acid (2.0 g, 14.5 mmol, exo,endo mixture)and dichloroethane (20 ml). To this stirred mixture at ambienttemperature was added a catalyst solution prepared by addingη³-allylpalladium chloride dimer (6 mg, 16 μmol) in dichloroethane (5ml) to silver hexafluoroantimonate (50 mg, 146 μmol) in dichloroethane(5 ml) for 30 minutes and then filtering through a micropore filter (toremove the precipitated silver chloride). The reaction was allowed torun for 18 hours at which time the mixture had gelled to form a clearyellow gel. Upon adding the gel to excess hexane the polymerprecipitated as a white powder. The polymer was washed with excesshexane and dried. The yield of polymer was 1.2 g (60%). The polymer wasfound to have a molecular weight (M_(w)) of 22,000 and a polydispersityof 2.3.

[0199] Upon adding a portion of this polymer (0.5 g) to an 0.1N stirredaqueous solution of KOH (10 ml) the polymer immediately dissolved togive a non-viscous, colorless solution. This demonstrates the basedevelopability of these materials since none of the homopolymers of thet-butylester of 5-norbornene-carboxylic acid showed any tendency todissolve under the same conditions.

EXAMPLE 19

[0200] The Pinner synthesis of ortho esters is a two-step synthesis:

[0201] Step 1. Synthesis of Imidic Ester Hydrochloride.

[0202] The reaction was carried out in a 1 L two-neck round-bottom flaskequipped with a stirrer, an oil bubbler, and a tube with anhydrouscalcium chloride. The following reagents were placed in the flask: 100 g(0.84 mol) norbornene carbonitrile (NB—CN), 37 ml (0.91 mol) anhydrousmethanol, and 200 mL anhydrous diethyl ether. The flask was placed intothe ice-water bath and 61 g (1.67 mol) dry hydrogen chloride was bubbledthrough the mixture with stirring during 1.5 hours. The flask was placedovernight in a refrigerator at 0° C. In the morning, the mixturesolidified into a “cake”. It was broken into pieces and additional 200ml of diethyl ether were added. The flask was kept in refrigerator foranother 10 days with occasional stirring. At the end of this period,precipitated imidic ester hydrochloride was filtered by suction andwashed 5 times with ˜300 mL diethyl ether. Ca. 20 g of unreacted NB—CNwere recovered from filtrate.

[0203] Yield of imidic ester hydrochloride—76% (120 g, 0.64 mol).Structure of the product was confirmed by ¹H NMR spectroscopy.

[0204] Step 2. Synthesis of Ortho Ester.

[0205] In a 0.5 L flask, 56.7 g (0.30 mol) imidic ester hydrochloride,37 ml (0.91 mol) anhydrous methanol, and 250 ml anhydrous petroleumether were placed. The reaction mixer was kept at room temperature for 5days with occasional stirring. Precipitated ammonium chloride wasfiltered off and washed with petroleum ether three times. Filtrate andwashes were combined, petroleum ether was distilled off, and product wasfractionally distilled in vacuum. A fraction with the boiling point68-69° C./3 mm Hg was collected. Yield—50% (30 g, 0.15 mol). Accordingto ¹H NMR spectrum, the product is 97+% 5-norbornene-2-trimethoxymethane(ortho ester).

EXAMPLE 20

[0206] To a solution of 2.16 g (10.9 mmol) C₇H₉C(OCH₃)₃ (norbornenetrimethylorthoester) in 16 ml 1,2-dichloroethane, was added a solutionof the reaction product of mixing 1 mole of allylpalladium chloridedimer with 2 moles of silver hexafluoroantimonate in dichloroethane andfiltering off the resulting silver chloride precipitate. The amount ofcatalyst added corresponded to 0.08 mmol of palladium dissolved in 2 mldichloroethant: The stirred reaction mixture was placed in an oil-bathat 70° C. and allowed to react for 20 hours.

[0207] At the end of the reaction, 2 ml methanol was added, solventsremoved on a rotary evaporator, and polymer dried to a constant weightin vacuum.

[0208] Yield—1.28 g (60%).

EXAMPLE 21

[0209] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded bicyclo[2.2.1]hept-5-ene-2-methyl acetate (18.44 g, 0.1109 mol)and t-butylester of norbornene (21.55 g, 0.1109 mol) and 75 ml oftoluene. A solution of the nickel catalyst [toluene complex ofbisperfluorophenyl nickel, (Tol)Ni(C₆F₅ ₂)] was prepared in the dry boxby dissolving 0.5367 g (1.109 mmol of (Tol)Ni(C₆F₅)₃] in 15 ml oftoluene. The active catalyst solution was added to the monomer solutionvia a syringe at ambient temperature. The reaction was allowed to stirfor 6 hours at room temperature. The solution was diluted with tolueneand the polymer was precipitated in excess methanol. The precipitatedpolymer was filtered, washed with acetone, and dried overnight undervacuum. The isolated yield of polymer was 24.9 g (63%). The polymer wascharacterized using GPC for molecular weight. Mn=21,000 and Mw=52,000.The NMR analysis of the copolymer indicated presence of 51 mole % of thet-butyl groups. IR analysis of the copolymer indicated the absence ofacid groups.

EXAMPLE 22

[0210] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded bicyclo[2.2.1]hept-5-ene-2-methyl ethylcarbonate (4.03 g, 0.0205mol) and t-butylester of norbornene (3.98 g, 0.0205 mol) and 50 ml oftoluene. A solution of the nickel catalyst [toluene complex ofbisperfluorophenyl nickel (Tol)Ni(C₆F₅)₂] was prepared in the dry box bydissolving 0.0991 g (0.2049 mmol of (Tol)Ni(C₆F₅)₂] in 15 ml of toluene.The active catalyst solution was added to the monomer solution via asyringe at ambient temperature. The reaction was allowed to stir for 6hours at room temperature. The solution was diluted with toluene and thepolymer was precipitated in excess methanol. The precipitated polymerwas filtered, washed with acetone and dried overnight under vacuum. Theisolated yield of polymer was 4.16 g (52%). The polymer wascharacterized using GPC for molecular weight. Mn=22,000 and Mw=58,000.The NMR analysis of the copolymer indicated presence of 50 mole % of thet-butyl groups. IR analysis of the copolymer indicated the absence ofacid groups.

EXAMPLE 23

[0211] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded bicyclo(2.2.1]hept-5-ene-2-methyl butylcarbonate (17.15 g, 0.0764mol) and t-butylester of norbornene (14.85 g, 0.0764 mol) and 72 ml oftoluene. A solution of the nickel catalyst toluene complex ofbisperfluorophenyl nickel, (Tol)Ni(C₆F₅)₂] was prepared in the dry boxby dissolving 0.3699 g (0.7644 mmol of(Tol)Ni(C₆F₅)₂] in 15 ml oftoluene. The active catalyst solution was added to the monomer solutionvia a syringe at ambient temperature. The reaction was allowed to stirfor 6 hours at room temperature. The solution was diluted with tolueneand the polymer was precipitated in excess methanol. The precipitatedpolymer was filtered, washed with acetone, and dried overnight undervacuum. The isolated yield of polymer was 17.53 (54%). The polymer wascharacterized using GPC for molecular weight. Mn=22,000 and Mw=58,000.The NMR analysis of the copolymer indicated presence of 54 mole % of thet-butyl groups. IR analysis of the copolymer indicated the absence ofacid groups.

EXAMPLE 24

[0212] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded t-butyl ester of norbornene (29.92 g, 0.154 mol), followed bydried maleic anhydride (15.10 g, 0.154 mol) and 90 ml of chlorobenzene.This mixture was degassed three times to remove any trace oxygen. Thereaction mixture was then heated to 80° C. A degassed benzoyl peroxidesolution consisting of 0.9948 g (0.04 mol) benzoyl peroxide free radicalinitiator in 10 ml of chlorobenzene was added to the reaction mixturewith a dry syringe. The reaction was left to stir for 19 hours. Afterthe reaction, the polymer solution was poured directly into hexane toprecipitate the polymer. A white precipitate was obtained. Theprecipitated polymer was then stripped out of any unreacted maleicanhydride that may have been present. The polymer was then driedovernight in a vacuum oven at room temperature. The weight of drypolymer obtained was 20.62 g, giving a 45.8% yield. The polymer wascharacterized using GPC for molecular weight. Mn=4,200 and Mw=8,800. TheNMR analysis of the copolymer indicated presence of the t-butyl groups.IR analysis of the copolymer indicated the presence of both t-butyl andmaleic anhydride groups.

EXAMPLE 25

[0213] To a 50 ml glass vial equipped with a Teflon® coated stir bar wasadded bicyclo[2.2.1]hept-5-ene-2-methyl acetate (13.3 g, 0.0799 mol),t-butyl ester of norbornene (15.70 g, 0.0808 mol), followed by driedmaleic anhydride (15.85 g, 0.162 mol) and 90 ml of chlorobenzene. Thismixture was degassed three times to remove any trace oxygen. Thereaction mixture was then heated to 80° C. A degassed benzoyl peroxidesolution consisting of 1.0438 g (0.041 mol) benzoyl peroxide freeradical initiator in 10 ml of chlorobenzene was added to the reactionmixture with a dry syringe. The reaction was left to stir for 19 hours.After the reaction, the polymer solution was poured directly into hexaneto precipitate the polymer. A white precipitate was obtained. Theprecipitated polymer was then stripped out of any unreacted maleicanhydride that may have been present. The polymer was then driedovernight in a vacuum oven at room temperature. The weight of drypolymer obtained was 21.89 g, giving a 48.7% yield. The polymer wascharacterized using GPC for molecular weight. Mn=3,000 and Mw=6600. TheNMR analysis of the copolymer indicated presence of the acetate andt-butyl groups. IR analysis of the copolymer indicated presence ofacetate, t-butyl and maleic anhydride groups.

EXAMPLE 26

[0214] (50:50 Copolymer of t-BuNBEster/NB-COOH)

[0215] To a 50 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added the t-butyl ester of norbornenecarboxylic acid (2 g, 10 mmol) and norbornene carboxylic acid (1.38 g,10 mmol). To this stirred mixture was added, at ambient temperature, theinitiator (t-butyl peroxide) (2.9 g) and the resulting mixture washeated to 130° C. and stirring was continued for 16 hours. The resultingpolymer (soluble in both THF and toluene) was precipitated into hexaneand filtered to afford the product, which on drying weighed 2.91 g (86%conversion). The resulting solid polymer exhibited an Mw of 20,000, Mn3,000). IR, NMR and TGA analysis of the copolymers confirmed theircomposition to be random addition copolymers of the two monomers.

EXAMPLE 27

[0216] (50:50 Copolymer of t-BuNBEster/NB-MeNBEster)

[0217] To a 50 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added the t-butyl ester of norbornenecarboxylic acid (2 g, 10 mmol) and the methyl ester of norbornenecarboxylic acid (1.5 g, 10 mmol). To this stirred mixture was added, atambient temperature, the initiator (t-butyl peroxide) (2.9 g) and theresulting mixture was heated to 130° C. and stirring was continued for16 hours. The resulting polymer (soluble toluene) was precipitated intomethanol and filtered to afford the product, which on drying weighed0.82 g (23% conversion). The resulting solid polymer exhibited an Mw of35,000, Mn 6,000). IR, NMR and TGA analysis of the copolymers confirmedtheir composition to be random addition copolymers of the two monomers.

EXAMPLE 28

[0218] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0219] To a 100 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added toluene (40 ml), t-butyl ester ofnorbornene carboxylic acid (1.94 g, 10 mmol) and ethyl ester oftetracyclododecene carboxylic acid (2.32 g, 10 mmol). To this stirredsolution was added, at ambient temperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (34 mg, 0.042mmol) in 5 ml of toluene. After 1 hour ethyl vinyl ether (0.015 ml,0.156 mmol) was added and stirred 1 hour. The polymer solution wasprecipitated by addition to excess MeOH, collected by filtration anddried under vacuum. Recovered 3.46 g (81% yield) of copolymer wasrecovered (Mw 221,000, Mn 133,000).

[0220] The copolymer was redissolved in toluene and passed through acolumn of silica gel with a resulting noticeable color (Ru) removal. Thepolymer was again precipitated in excess MeOH rendering a pure whitecopolymer.

EXAMPLE 29

[0221] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0222] To a 100 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added toluene (80 ml), t-butyl ester ofnorbornene carboxylic acid (3.9 g, 20 mmol) and ethyl ester oftetracyclododecene carboxylic acid (4.64 g, 20 mmol). To this stirredsolution was added, at ambient temperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (68 mg, 0.083mmol) in 5 ml of toluene. After 2 hours ethyl vinyl ether (0.030 ml,0.31 mmol) was added and stirred 2 hours.

[0223] The orange-amber solution was passed through silica gel column toobtain a clear colorless solution. The solution was precipitated byaddition of excess MeOH, collected by filtration and dried under vacuum.6.54 g (77% yield) of copolymer was recovered (Mw 244,000, Mn 182,000).The glass transition temperature was measured using DSC methods anddetermined to be 220° C.

EXAMPLE 30

[0224] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0225] To a 300 ml stainless steel reactor equipped with a mechanicalstirrer and containing nitrogen was added toluene (90 ml), t-butyl esterof norbornene carboxylic acid (3.9 g, 20 mmol) and ethyl ester oftetracyclododecene carboxylic acid (4.64 g, 20 mmol). To this stirredsolution was added, at ambient temperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (68 mg, 0.083mmol) in 5 ml of toluene. After 2 hours ethyl vinyl ether (0.030 ml,0.31 mmol) was added and stirred 16 hours. Hydrogen (350 psig) was addedto reactor and the temperature was maintained at 175° C. for 7 hours.Following reaction the solution was passed through a silica gel columnand the hydrogenated copolymer was isolated. NMR methods were used todetermine that the copolymer was 95% hydrogenated (Mw 237,000, Mn163,000).

EXAMPLE 31

[0226] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0227] To a 300 ml stainless steel reactor equipped with a mechanicalstirrer and containing nitrogen was added toluene (90 ml), t-butyl esterof norbornene carboxylic acid (2.9 g, 15 mmol) and ethyl ester oftetracyclododecene carboxylic acid (3.5 g, 15 mmol). To this stirredsolution was added, at ambient temperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (50 mg, 0.060mmol) in 5 ml of toluene. After 2 hours hydrogen (800 psig) was added toreactor and temperature maintained at 175° C. for 7 hours. Followingreaction the solution was passed through silica gel column and thehydrogenated coplymer was isolated. NMR methods were used to determinethat the copolymer was 96% hydrogenated (Mw 278,000, Mn 172,000).

EXAMPLE 32

[0228] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0229] To a 100 ml glass vial equipped with a magnetic stirring bar andcontaining nitrogen was added toluene (40 ml), t-butyl ester ofnorbornene carboxylic acid (1.94 g, 10 mmol), ethyl ester oftetracyclododecene carboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.050ml, 0.4 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (34 mg, 0.042mmol) in 5 ml of toluene. After 2 hours the polymer solution was addedto an excess of MeOH, collected by filtration and dried under vacuum.3.1 g (73% yield) of polymer was recovered (Mw 35,000, Mn 22,000).

EXAMPLE 33

[0230] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0231] To a 100 ml glass vial equipped with a magnetic stirring bar andcontaining nitrogen was added toluene (40 ml), t-butyl ester ofnorbornene carboxylic acid (1.94 g, 10 mmol), ethyl ester oftetracyclododecene carboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.275ml, 2.2 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (34 mg, 0.042mmol) in 5 ml of toluene. After 2 hours the polymer solution was addedto an excess of MeOH, collected by filtration and dried under vacuum.3.45 g (81% yield) of polymer was recovered (Mw 8,000, Mn 6,000).

EXAMPLE 34

[0232] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0233] To a 100 ml glass vial equipped with a magnetic stirring bar andcontaining nitrogen was added toluene (40 ml), 1-butyl ester ofnorbornene carboxylic acid (1.94 g, 10 mmol), ethyl ester oftetracyclododecene carboxylic acid (2.32 g, 10 mmol) and 1-hexene (0.62ml, 5.0 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricycloheylphosphine)benzylideneruthenium dichloride (34 mg, 0.042mmol) in 5 ml of toluene. After 2 hours the polymer solution was addedto an excess of MeOH, collected by filtration and dried under vacuum.2.75 g (65% yield) of polymer was recovered.

EXAMPLE 35

[0234] (50:50 Copolymer of t-BuNBEster/EtTDEster)

[0235] To a 100 ml glass vial equipped with a magnetic stirring bar andcontaining nitrogen was added toluene (80 ml), t-butyl ester ofnorbornene carboxylic acid (3.9 g, 20 mmol), ethyl ester oftetracyclododecene carboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088ml, 0.7 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (68 mg, 0.083mmol) in 5 ml of toluene. After 2 hours ethyl vinyl ether (0.030 ml,0.31 mmol) was added and stirred 2 hours.

[0236] The orange-amber polymer solution was passed through silica gelcolumn which removed the dark color (Ru). The solution was precipitatedby addition to excess MeOH, collected by filtration and dried overnightat 80° C. under vacuum. 2.6 g (30% yield) of polymer was recovered (Mw4,000, Mn 3,000).

EXAMPLE 36

[0237] (50:50 Copolymer of t-BuNBEster/EtTDEster,)

[0238] To a 300 ml stainless steel reactor equipped with a mechanicalstirrer and containing nitrogen was added toluene (80 ml), t-butyl esterof norbornene carboxylic acid (3.9 g, 20 mmol), ethyl ester oftetracyclododecene carboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088ml, 0.7 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (68 mg, 0.042mmol) in 5 ml of toluene. After 2 hours hydrogen (750 psig) was added toreactor and temperature maintained at 175° C. for 20 hours.

[0239] The solution was precipitated by addition to excess methanol,collected by filtration and dried overnight at 80° C. under vacuum.Approximately 5 g (59% yield) of polymer was recovered (Mw 30,000, Mn20,000). NMR methods were used to determine that the copolymer wasgreater than 99% hydrogenated.

EXAMPLE 37

[0240] (65:35 Copolymer of t-BuNBEster/EtTDEster)

[0241] To a 250 ml round bottomed flask equipped with a magneticstirring bar and containing nitrogen was added toluene (160 ml), t-butylester of norbornene carboxylic acid (10.1 g, 52 mmol), ethyl ester oftetracyclododecene carboxylic acid (6.5 g, 28 mmol) and 1-hexene (0.176ml, 1.4 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (131 mg,0.160 mmol) in 5 ml of toluene. After 16 hours ethyl vinyl ether (0.060ml, 0.62 mmol) was added and stirred 1.5 hours. The polymer solution waspassed through silica gel column to remove Ru. The solution was added toan excess of methanol collected by filtration and dried under vacuum.9.69 g (58% yield) of polymer was recovered (Mw 42,000, Mn 31,000). DSCmethods were used to measure the glass transition temperature (110° C.).

EXAMPLE 38

[0242] In a 100 no glass vial containing nitrogen was dissolved 5.0 g ofthe polymer from Example 37 in THF (80 ml). The solution was transferredto a 300 ml stainless steel reactor. 2.25 g of S wt % palladium onalumina catalyst (purchased from Aldrich) was added to reactor. Thereactor was then heated to 175° C. and pressurized with 800 psighydrogen. Temperature and pressure were maintained for 9.5 hrs. Theresulting polymer solution was centrifuged and the colorless solutionwas separated and the polymer was precipitated in excess methanol. NMRmethods showed the resulting copolymer to be greater than 99%hydrogenated.

EXAMPLE 39

[0243] (50:50 Copolymer of t-BuNBEster/EtTDEster,)

[0244] To a 100 ml glass vial. equipped with a magnetic stirring bar andcontaining nitrogen was added toluene (80 ml), t-butyl ester ofnorbornene carboxylic acid (3.9 g, 20 mmol), ethyl ester oftetracyclododecene carboxylic acid (4.64 g, 20 mmol) and 1-hexene (0.088ml, 0.7 mmol). To this stirred solution was added, at ambienttemperature, a solution ofbis(tricyclohexylphosphine)benzylideneruthenium dichloride (68 mg, 0.084mmol) in 5 ml of toluene. After 2 hours ethyl vinyl ether (30 μl) wasadded to the reaction to short stop further reactions and the mixturewas stirred for 1.5 hours. The polymer solution was passed through asilica gel column to remove Ru residues and the polymer was thenrecovered as a clean white solid by precipitating into methanol. Thepolymer was found to have an Mw of 46,600 (Mn 33,700) and was fullycharacterized by IR, NMR and TGA methods.

EXAMPLE 40

[0245] To a stainless steel autoclave with an internal volume of 300 mlwas added ethyl 2-methyl-4-pentenoate (99 g, 0.7 mole) and freshlycracked cyclopentadiene (46.4 g, 0.7 mole). The stirred mixture washeated to 200° C. and left overnight. The reactor was then cooled andthe contents removed. The resulting functionalized norbornene(NB—CH₂CH(CH₃)C(O)OC₂H₅) was purified by vacuum distillation and foundto have a boiling point of about 46-7° C. at 0.02 mm Hg. The materialwas analyzed by GC methods and found to have a purity of 98.4 to 99.3%(different fractions). The isolated yield of high purity product wasaround 33 g.

EXAMPLE 41

[0246] (40:60 Copolymer of t-BuNBEster (NB—CH₂CH(CH₃)C(O)OC₂H₅))

[0247] To a 100 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added toluene (5.0 ml), t-butyl ester ofnorbornene carboxylic acid (2.7 g, 14 mmol) and the ester from Example40 (NB—CH₂CH(CH₃)C(O)OC₂H₅) (4.4 g, 21 mmol). To this stirred solutionwas added, at ambient temperature, a solution of (toluene)Ni(C₆F₅)₂ intoluene (1 ml) and the resulting solution was heated to 50° C. andstirring was continued for 3 hours. The polymer was precipitated intomethanol and filtered. The resulting solid was then redissolved in THF,filtered and precipitated again with methanol and filtered. Theresulting white solid polymer was dried and found to weigh 2.66 g (Mw70,000; Mn 39,800), the supernatant was evaporated to dryness to afforda further crop of white polymer which on drying weighed 1.52 g (Mw60,650; Mn 31,000). The total yield of copolymer represented 59%conversion of the monomers. IR, NMR and TGA analysis of the copolymersconfirmed their composition to be random addition copolymers of the twomonomers.

EXAMPLE 42

[0248] (40:60 Copolymer of t-BuNBEster (NB—CH₂CH(CH₃)C(O)OC₂H₅)

[0249] To a 250 ml glass vial equipped with a magnetic stirring bar andunder a nitrogen atmosphere was added dichloroethane (200 ml), t-butylester of norbornene carboxylic acid (7.76 g, 40 mmol) and the ester fromExample 40 (NB—CH₂CH(CH₃)C(O)OC₂H₅) (12.5 g, 60 mmol) and2,6-di-t-butylpyridine (28.8 mg, 0.26 mmol). To this stirred solutionwas added, at ambient temperature, a solution of the catalyst resultingfrom mixing allylpalladium chloride dimer (0.183 g, 0.5 mmol) withsilver hexafluoroantimonate (equivalent amount) in dichloroethane (3 ml)and filtering to remove the silver chloride precipitate. The resultingsolution was heated to 50° C. and stirring was continued for 16 hours.The polymer solution was treated with carbon monoxide (4 psi pressure)for 48 hours to precipitate the palladium residues, filtered through a0.45μ filter, reduced in volume and precipitated with excess methanol toafford 7.9 g of the copolymer (39% conversion), Mw 11,600, Mn 7,000. Thecopolymer was fully characterized using IR, NMR and TGA methods.

EXAMPLE 43

[0250] Copolymerization of CO and norbornene-5-t-butylester

[0251] A deoxygenated methanol solution of bipyridine (0.025 g, 0.16mmol) was added to palladium (II) acetate (0.012 g, 0.053 mmol)dissolved in deoxygenated methanol. To this solution was addedp-toluenesulfonic acid (0.045 g, 0.27 mmol) dissolved in deoxygenatedmethanol. The resulting brown solution was added to a methanol(deoxygenated) solution of benzoquinone (1.72 g, 1.59 mmol). This wasadded to a stainless steel reactor preheated to 50° C. To this reactorwas added norbornene-5-t-butylester (5.14 g, 0.027 mol) in 100 ml ofMeOH (deoxygenated with argon). The reactor was pressurized with carbonmonoxide to 600 psig and warmed to 65° C. After 4.5 hours, the carbonmonoxide was vented and the reactor was allowed to cool. The pinksolution from the reactor was filtered to remove palladium residues andallowed to evaporate. The resulting mixture was dissolved in a minimumof THF and poured slowly into a 25:75 mixture of water:methanol toprecipitate the polymer. This procedure was repeated twice. Theresulting white polymer was filtered and dried at room temperature undervacuum. Yield=2.9 g.

EXAMPLE 43A

[0252] A deoxygenated, dried THF/methanol (35 ml/15 ml) solution ofbenzoquinone (0.43 g, 0.40 mmol), bipyridine (0.0062 g, 0.0040 mmol),and Pd(MeCN)₂(p-toluenesulfonate) (0.0070 g, 0.0013 mmol) was added to adry 5001 ml stainless steel reactor warmed to 50° C. To the reactor wasadded norbornene-5-t-butylester (5.14 g, 0.027 mol) in 100 ml of THF(deoxygenated and dried). The reactor was pressurized with carbonmonoxide to 600 psig and warmed to 65° C. After 12.5 hours, the reactorwas heated to 90° C. for 1.5 hours. Then the carbon monoxide was ventedand the reactor was allowed to cool. The purple solution from thereactor was filtered to remove palladium residues and allowed toevaporate. The resulting mixture was dissolved in a minimum of THF andpoured slowly into a 25:75 mixture of water:methanol to precipitate thepolymer. This procedure was repeated twice. The resulting white polymerwas filtered and dried at room temperature under vacuum. Yield 2.9 g.

EXAMPLES 44 TO 50

[0253] Optical Density Measurements for Cyclic Olefin Based Homo andCopolymers at 193 nm

[0254] Optical density is a critical characteristic of an effectivephotoresist because it determines the uniformity of the energythroughout the film thickness. A typical, lithographically useful,polymer backbone has an optical density of less than 0.2 absorbanceunits/micron prior to the addition of photoacid generators. (T. Neenan,E. Chandross, J. Kometani and O. Nalamasu, “Styrylmethylsulfonamides:Versatile Base-Solubilizing Components of Photoresist Resins” pg. 199 inMicroelectronics Technology, Polymers for Advanced Imaging andPackaging, ACS Symposium Series 614, Eds: E. Reichmanis, C. Ober, S.MacDonald, T. Iwayanagai and T. Nishikubo, April, 1995).Polyhydroxystyrene, the primary component of typical 248 nm DUVphotoresists, has an optical density of 2.8 absorbance units/micron at193 nm and hence is unusable as a resist backbone at this wave length.

[0255] Preparing Sample Solution

[0256] Samples of various polymers set forth in the foregoing examples(0.016±0.001 g of polymer) were weighed out and dissolved in 4 ml ofchloroform. The solutions of the polymers were removed by pipette andthin films were cast on clean uniform quartz slides. The films wereallowed to dry overnight. The resulting circular films on the quartzslides were further dried at 70° C. in an oven for 10 minutes under anitrogen purge.

[0257] UV spectra of the films were obtained using a Perkin-Elmer Lambda9 UV/VIS/IR spectrophotometer, at a scan speed of 120 nm/minute. Thespectrum range was set at 300 nm to 180 nm. By measuring the absorbanceof the films at 193 nm and normalizing them to the thickness of thefilms, the optical density of the films at 193 nm were measured. Theresults are set forth in the Table below: Film Normalized AbsorbanceThickness Absorbance at 193 Example Polymer at 193 nm (A) (microns) nm(Å/micron) 44 50/50 Copolymer of bicyclo[2.2.1]hept-5-ene-2- 1.017325.39 0.0400 methyl acetate/t-butylester of norbornene (polymer ofExample 21) 45 50/50 Copolymer of bicyclo[2.2.1]hept-5-ene-2-methyl0.1799 30.47 0.0059 ethyl carbonate/t-butylester of norbornene (polymerof Example 22) 46 50/50 Copolymer of bicyclo[2.2.1]hept-5-ene-2-methyl0.2808 33.01 0.0085 butyl carbonate/t-butylester of norbornene (polymerof Example 23) 47 Copolymer of maleicanhydride/t-butylester ofnorbornene 1.1413 38.09 0.0299 (polymer of Example 24) 48 Terpolymer ofbicyclo[2.2.1]hept-5-ene-2-methyl acetate/ 0.8433 17.78  0.04743maleicanhydride/t-butylester of norbornene (polymer of Example 25) 4950/50 copolymer of t-butyl ester of norbornene/ethyl 0.4693 33.01 0.0142ester of tetracyclododecene (polymer of Example 29) 50 50/50 copolymerof t-butyl ester of norbornene/ethyl 0.4146 35.55 0.0117 ester oftetracyclododecene (polymer of Example 30)

[0258] Preparation of Resist Solution, Exposure and Development:

[0259] The polymers obtained in the above examples were dissolved inpropylene glycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids,to which was added the onium salt set forth in the examples at 5 or 10w/w % to the polymer.

[0260] The solutions were filtered through a 0.2μ Teflon® filter. Aresist layer was formed from each solution by spin coating it onto ahexamethyldisilazane (HMDS) primed silicon wafer. The coated film wasbaked at 95° C. for 1 minute. The films were then exposed through aquartz mask to UV radiation from a Karl Suss MJB3 UV 250 instrumentbetween the wave lengths of 230 to 250 nm. The exposed films were heatedto 125° C. to 150° C. for 1 minute. The exposed and heated films werethen developed in aqueous base to provide high resolution positive toneimages without loss of film thickness in the unexposed regions.

[0261] The systems can be easily made negative working by development ina nonpolar solvent. These materials can be sensitized to the longer wavelengths (365 nm) by adding a small amount of sensitizers such as pyrene,perylene, or thioxanthones or to shorter wave lengths (193 nm), as thesematerials have been observed (as shown above) to have very low opticaldensity at 193 nm.

EXAMPLE 51

[0262] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylacetate/t-butylester of norbornene (the polymer of Example 21) numberaverage molecular weight 21,000) was dissolved in propylene glycolmonomethyl ether acetate (PGMEA) at 10 w/v % of solids.Triphenylsulfonium hexafluoroarsenate was added at a loading of 10 w/w %to the polymer. The resist film was filtered through a 0.2μ Teflon®filter and the filtered solution was spin coated from the solution ontoa hexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.7μ thicklayer. The film was baked at 95° C. for 1 min over a hot plate and thenexposed through a quartz mask to UV radiation (240 nm) at a dose of 50mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 52

[0263] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylacetate/t-butylester of norbornene (the polymer of Example 21) (numberaverage molecular weight 21,000) was dissolved in propylene glycolmonomethyl ether acetate (PGMEA) at 10 w/v % of solids. Diaryl iodoniumhexafluoroantimonate (Sartomer 1012) was added at a loading of 10 w/w %to the polymer. The resist film was filtered through a 0.2μ Teflon®filter and the filtered solution was spin coated from the solution ontoa hexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.7μ thicklayer. The film was baked at 95° C. for 1 min over a hot plate and thenexposed through a quartz mask to UV radiation (240 nm) at a dose of 50mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 53

[0264] Copolymer of bicyclo[2.2.1]hept-5-ene-2-methylacetate/t-butylester of norbornene (the polymer of Example 21) (numberaverage molecular weight 21,000) was dissolved in propylene glycolmonomethyl ether acetate (PGMEA) at 10 w/v % of solids. Diaryl iodoniumhexafluoroantimonate (Sartomer 1012) was added at a loading of 10 w/w %to the polymer. The resist film was filtered through a 0.2μ Teflon®filter and the filtered solution was spin coated from the solution ontoa hexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.7μ thicklayer. The film was baked at 95° C. for 1 min over a hot plate and thenexposed through a quartz mask to UV radiation (240 nm) at a dose of 100mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 54

[0265] Copolymer of bicyclo[2.2.1]hept-5-ene-2-methylacetate/t-butylester of norbornene (the polymer of Example 21) (numberaverage molecular weight 21,000) was dissolved in propylene glycolmonomethyl ether acetate (PGMEA) at 10 w/v % of solids.Triphenylsulfonium hexafluoroarsenate was added at a loading of 10 w/w %to the polymer. The resist film was filtered through a 0.2 p Teflon®filter and the filtered solution was spin coated from the solution ontoa hexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.7μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of10 mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 55

[0266] Copolymer of bicyclo[2.2.1]hept-5-ene-2-methylacetate/t-butylester of norbornene (the polymer of Example 21) (numberaverage molecular weight 21,000) was dissolved in propylene glycolmonomethyl ether acetate (PGMEA) at 10 w/v % of solids.Triphenylsulfonium hexafluoroarsenate was added at a loading of 10 w/w %to the polymer. The resist film was filtered through a 0.2μ Teflon®filter and the filtered solution was spin coated from the solution ontoa hexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.7μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 56

[0267] The copolymer of maleicanhydride/t-butylester of norborneneobtained via free radical polymerization (the polymer of Example 24)(number average molecular weight 4,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution inpropylene carbonate) was added at a loading of 5 w/w % to the polymer.The resist film was filtered through a 0.2μ Teflon® filter and thefiltered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.6 p thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 125° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base-for 60seconds.

EXAMPLE 57

[0268] The copolymer of maleic anhydride/t-butylester of norborneneobtained via free radical polymerization (the polymer of Example 24)(number average molecular weight 4,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 500/o solutionin propylene carbonate) was added at a loading of 5 w/w % to thepolymer. The resist film was filtered through a 0.2μ Teflon® filter andthe filtered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 0.6μ thicklayer. The-film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 95° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 58

[0269] The terpolymer of maleicanhydridetbicyclo[2.2.1]hept-5-ene-2-methyl acetate/t-butylester ofnorbornene obtained via free radical polymerization (the polymer ofExample 25) (number average molecular weight 3000) was dissolved inpropylene glycol monomethyl ether acetate (PGMEA) at 10 w/v % of solids.Diaryl iodonium hexafluoroantimonate (Sartomer 1012) was added at aloading of 10 w/w % to the polymer. The resist film was filtered througha 0.2μ Teflon® filter and the filtered solution was spin coated from thesolution onto a hexamethyldisilazane primed silicon wafer at 500 rpm for30 seconds followed by 2000 rpm for 25 seconds. This resulted in a 0.5μthick layer. The film was baked at 95° C. for 1 minute over a hot plateand then exposed through a quartz mask to UV radiation (240 nm) at adose of 50 mJ/cm². After post-baking at 125° C. for 1 minute, highresolution positive images were obtained by development in aqueous basefor 60 seconds.

EXAMPLE 59

[0270] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylethylcarbonate/t-butylester of norbornene (the polymer of Example 22)(number average molecular weight 22,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50%/o solutionin propylene carbonate) was added at a loading of 5 w/w % to thepolymer. The resist film was filtered through a 0.2μ Teflon® filter andthe filtered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 1.1μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 95° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 60

[0271] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylethylcarbonate/t-butylester of norbornene (the polymer of Example 22)(number average molecular weight 22,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triphenylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solutionin propylene carbonate) was added at a loading of 5 w/w % to thepolymer. The resist film was filtered through a 0.2μ Teflon® filter andthe filtered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 1.1μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of15 mJ/cm². After post-baking at 95° C. for 1 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 61

[0272] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylbutylcarbonate/t-butylester of norbornene (the polymer of Example 23)(number average molecular weight 22,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution inpropylene carbonate) was added at a loading of 5 w/w % to the polymer.The resist film was filtered through a 0.2μ Teflon® filter and thefiltered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 1.0μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 125° C. for 0.5 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 62

[0273] The copolymer of bicyclo[2.2.1]hept-5-ene-2-methylbutylcarbonate/t-butylester of norbornene (the polymer of Example 23)(number average molecular weight 22,000) was dissolved in propyleneglycol monomethyl ether acetate (PGMEA) at 15 w/v % of solids.Triarylsulfonium hexafluoroantimonate (Sartomer CD 1010, 50% solution inpropylene carbonate) was added at a loading of 5 w/w % to the polymer.The resist film was filtered through a 0.2 1 Teflon® filter and thefiltered solution was spin coated from the solution onto ahexamethyldisilazane primed silicon wafer at 500 rpm for 30 secondsfollowed by 2000 rpm for 25 seconds. This resulted in a 1.0μ thicklayer. The film was baked at 95° C. for 1 minute over a hot plate andthen exposed through a quartz mask to UV radiation (240 nm) at a dose of30 mJ/cm². After post-baking at 150° C. for 0.5 minute, high resolutionpositive images were obtained by development in aqueous base for 60seconds.

EXAMPLE 63

[0274] A 35/65 mole % hydrogenated copolymer of ethylester oftetracyclodecene/t-butylester of norbornene (the polymer of Example 37)(number average molecular weight 23,000) obtained via ring openingmetathesis polymerization was dissolved in propylene glycol monomethylether acetate (PGMEA) at 15 w/v % of solids. Triarylsulfoniumhexafluoroantimonate (Sartomer CD 1010, 50% solution in propylenecarbonate) was added at a loading of 5 w/w % to the polymer. The resistfilm was filtered through a 0.2μ Teflon® filter and the filteredsolution was spin coated from the solution onto a hexamethyldisilazaneprimed silicon wafer at 500 rpm for 30 seconds followed by 2000 rpm for25 seconds. This resulted in a 1.1μ thick layer. The film was baked at95° C. for 1 minute over a hot plate and then exposed through a quartzmask to UV radiation (240 nm) at a dose of 30 mJ/c. After post-baking at125° C. for 1.0 minute, high resolution positive images were obtained bydevelopment in aqueous base for 30 seconds.

EXAMPLE 64

[0275] A 50/50 mole % nonhydrogenated copolymer of ethylester oftetracyclodecene/t-butylester of norbornene (the polymer of Example 39)(number average molecular weight 34,000) obtained via ring openingmetathesis polymerization was dissolved in propylene glycol monomethylether acetate (PGMEA) at 15 w/v % of solids. Triarylsulfoniumhexafluoroantimonate (Sartomer CD 1010, 50% solution in propylenecarbonate) was added at a loading of 5 w/w % to the polymer. The resistfilm was filtered through a 0.2μ Teflon® filter and the filteredsolution was spin coated from the solution onto a hexamethyldisilazaneprimed silicon wafer at 500 rpm for 30 seconds followed by 2000 rpm for25 seconds. This resulted in a 1.25μ thick layer. The film was baked at95° C. for 1 minute over a hot plate and then exposed through a quartzmask to UV radiation (240 nm) at a dose of 50 mJ/cm². After post-bakingat 150° C. for 30 seconds, high resolution positive images were obtainedby development in aqueous base for 60 seconds.

We claim:
 1. A photoresist composition comprising a photoacid initiator,an optional dissolution inhibitor, and a polymer comprising polycyclicrepeating units at least a portion of which contain pendant acid labilegroups.
 2. The composition of claim 1 wherein said polymer ispolymerized from one or more acid labile group substituted polycyclicmonomer(s) in optional combination with a monomer selected from thegroup consisting of a neutral group substituted polycyclic monomer, acarboxylic acid group substituted polycyclic monomer, an alkylsubstituted polycyclic monomer, and mixtures thereof wherein said acidlabile group monomer is represented by the structure:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)—OC(O)OR, or —(CH₂)_(n)—C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂,subject to the proviso that at least one of R¹ to R⁴ is selected fromthe acid labile group —(CH₂)_(n)—C(O)OR*, R represents hydrogen orlinear and branched (C₁ to C₁₀) alkyl, m is an integer from 0 to 5 and nis an integer from 0 to 10, and R* represents a moiety that is cleavableby a photoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranyl 3-oxocyclohexanyl, mevalonic lactonyl,dicyclopropylmethyl, and dimethylpropylmethyl, R** independentlyrepresents R and R*; wherein said neutral group substituted monomer isrepresented by the structure:

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)(C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl, monocyclic and polycyclic (C₄ toC₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to10; wherein said carboxylic group containing monomer is represented bythe structure:

wherein R⁹ to R¹² independently represent hydrogen, linear and branched(C₁ to C₁₀) alkyl and a carboxylic substituent represented by theformula —(CH₂)_(n)C(O)OH, with the proviso that at least one of R⁹ toR¹² is a carboxylic substituent, q is an integer from 0 to 5, and n isan integer from 0 to 10; and wherein said alkyl substituted monomer isrepresented by the structure:

wherein R¹³ to R¹⁶ independently represent hydrogen or linear orbranched (C₁ to C₁₀) alkyl, with the proviso that at least one of R¹³ toR¹⁶ is (C₁ to C₁₀) alkyl, and r is an integer from 0 to
 5. 3. Thecomposition of claim 2 wherein said monomers are polymerized byring-opening polymerization to obtain a ring-opened polymer.
 4. Thecomposition of claim 3 wherein said ring-opened polymer is hydrogenated.5. The composition of claim 2 wherein said monomers are polymerized byfree radical polymerization.
 6. The composition of claim 2 wherein saidmonomers are polymerized in the presence of a catalyst selected from thegroup consisting of a single component or multicomponent catalyst systemeach comprising a Group VIII metal ion source wherein said singlecomponent catalyst is represented by the formulae: E_(n)Ni(C₆F₅)₂[L_(y)MX_(z)][CA]_(a) Pd[R²⁷CN]₄[CA⁻]₂ wherein in the formulae above, Erepresents a neutral 2 electron donor ligand, n is 1 or 2; L representsa ligand containing between 1, 2, or 3 π-bonds; M represents palladiumor nickel; X represents a ligand containing 1 σ-bond and between 0 to 3π-bonds; y is 0, 1, or 2 and z is 0 or 1, and wherein y and z cannotboth be 0 at the same time, and when z is 0, a is 2, and when z is 1, ais 1; R²⁷ independently represents linear and branched (C₁ to C₁₀)alkyl;and CA is a counteranion selected from the group consisting of BF₄ ⁻;PF₆ ⁻, AlF₃O₃SCF₃ ⁻;, SbF₆ ⁻; SbF₅SO₃F⁻, AsF₆ ⁻, perfluoroacetate(CF₃CO₂ ⁻), perfluoropropionate (C₂F₅CO₂ ⁻), perfluorobutyrate(CF₃CF₂CF₂CO₂ ⁻), perchlorate (ClO₄ ⁻.H₂O), p-toluene-sulfonate(p-CH₃C₆H₄SO₃ ⁻) and tetraphenylborates represented by the formula:

wherein R″ independently represents hydrogen, fluorine andtrifluoromethyl and n is 1 to 5; and wherein said multicomponentcatalyst comprises: (a) a Group VIII metal ion source in combinationwith one or both of; (b) an organometal cocatalyst compound; (c) a thirdcomponent selected from the group consisting of Lewis acids, strongBrønsted acids, halogenated compounds, electron donating compoundsselected from aliphatic and cycloaliphatic diolefins, and mixturesthereof.
 7. The composition of claim 6 wherein said Lewis acids areselected from the group consisting of BF₃-etherate, TiCl₄, SbF₅, BCl₃,B(OCH₂CH₃)₃, and tris(perfluorophenyl) boron, said strong Brønsted acidsare selected from the group consisting of HSbF₆, HPF₆, CF₃CO₂H,FSO₃H.SbF₅, H₂C(SO₂CF₃)₂, CF₃SO₃H and paratoluenesulfonic acid; and saidhalogenated compounds are selected from the group consisting ofhexachloroacetone, hexafluoroacetone, 3-butenoicacid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid,hexafluoroisopropanol and chloranil; wherein said electron donatingcompounds are selected from aliphatic and cycloaliphatic diolefins,phosphines and phosphites, and mixtures thereof.
 8. The composition ofclaim 6 wherein the organometal compound is selected from the groupconsisting organoaluminum compounds, dialkyl zinc compounds, dialkylmagnesium, alkyllithium compounds, and mixtures thereof.
 9. Thecomposition of claim 6 wherein E is selected from the group consistingof toluene, benzene, mesitylene, THF, and dioxane.
 10. The compositionof claim 9 wherein the catalyst is selected from the group consisting of(toluene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl)nickel, (mesitylene)bis(perfluorphenyl) nickelbis(tetrahrydrofuran)bis(perfluorophenyl) nickel, andbis(dioxane)bis(perfluorophenyl) nickel.
 11. The composition of claim 1wherein said polymer comprises repeating units selected from thestructure:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)—OC(O)OR, —(CH₂)_(n)—C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂(CH(C(O)OR**)₂,subject to the proviso that at least one of R¹ to R⁴ is selected fromthe acid labile group —(CH₂)_(n)—C(O)OR*, R represents hydrogen orlinear and branched (C₁ to C₁₀) alkyl m is an integer from 0 to 5 and nis an integer from 0 to 10, and R* represents a moiety that is cleavableby a photoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl,dicyclopropylmethyl, and dimethylpropylmethyl, R** independentlyrepresents R and R*.
 12. The composition of claim 11 wherein saidpolymer further comprises at least one repeating unit selected from thegroup represented as follows:

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)(C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) allyl, monocyclic and polycyclic (C₄ to C₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl p is an integer from 0 to 5, and n is an integer from 0 to10; R⁹ to R¹² independently represent hydrogen, linear and branched (C₁to C₁₀) alkyl and a carboxylic substituent represented by the formula—(CH₂)_(n)C(O)OH, with the proviso that at least one of R⁹ to R¹² is acarboxylic substituent, q is an integer from 0 to 5, and n is an integerfrom 0 to 10; and R¹³ to R¹⁶ independently represent hydrogen or linearor branched (C₁ to C₁₀) alkyl, with the proviso that at least one of R¹³to R¹⁶ is (C₁ to C₁₀) alkyl, and r is an integer from 0 to
 5. 13. Thecomposition of claim 9 wherein said monomers are polymerized in thepresence of a catalyst selected from the group consisting of(toluene)bis(perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl)nickel, (benzene)bis(perfluorophenyl) nickel,bis(tetrahydrofuran)bis(perfluorophenyl) nickel, andbis(dioxane)bis(perfluorophenyl) nickel.
 14. The composition of claim 1wherein said polymer comprises repeating units selected from thestructure:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)—OC(O)OR, —(CH₂)_(n)—C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂ subjectto the proviso that at least one of R¹ to R⁴ is selected from the acidlabile group —(CH₂)_(n)C(O)OR*, R represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl, m is an integer from 0 to 5 and n is aninteger from 0 to 10, and R* represents a moiety that is cleavable by aphotoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahrydopyranyl, 3-oxocyclohexanyl, mevalonic lactonyl,dicyclopropylmethyl, and dimethylpropylmethyl, R** independentlyrepresents R and R*.
 15. The composition of claim 14 wherein saidpolymer further comprises at least one repeating unit selected from thegroup represented as follows:

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)(C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl, monocyclic and polycyclic (C₄ toC₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to10; R⁹ to R¹² independently represent hydrogen, linear and branched (C₁to C₁₀) alkyl, and a carboxylic substituent represented by the formula—(CH₂)C(O)OH, with the proviso that at least one of R⁹ to R¹² is acarboxylic substituent, q is an integer from 0 to 5, and n is an integerfrom 0 to 10; and R¹³ to R¹⁶ independently represent hydrogen or linearor branched (C₁ to C₁₀) alkyl, with the proviso that at least one of R¹³to R¹⁶ is (C₁ to C₁₀) alkyl, and r is an integer from 0 to
 5. 16. Thecomposition of claim 1, 2, 11, 12, 14 or 15 wherein said polymer has apendant perfluorophenyl group at at least one terminal end thereof. 17.The composition of claim 1 wherein said polymer comprises repeatingunits selected from the structure:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)OC(O)OR, or —(CH₂)_(n)C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂,subject to the proviso that at least one of R¹ to R⁴ is selected fromthe acid labile group —(CH₂)_(n)—C(O)OR*, R represents hydrogen orlinear and branched (C₁ to C₁₀) alkyl, m is an integer from 0 to 5 and nis an integer from 0 to 10, and R* represents a moiety that is cleavableby a photoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyldicyclopropylmethyl and dimethylpropylmethyl R** independentlyrepresents R and R*.
 18. The composition of claim 17 wherein saidpolymer further comprises at least one repeating unit selected from thegroup represented as follows:

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)(C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl monocyclic and polycyclic (C₄ toC₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to10; R⁹ to R¹² independently represent hydrogen, linear and branched (C₁to C₁₀) alkyl and a carboxylic substituent represented by the formula—(CH₂)_(n)C(O)OH, with the proviso that at least one of R⁹ to R¹² is acarboxylic substituent, q is an integer from 0 to 5, and n is an integerfrom 0 to 10; and R¹³ to R¹⁶ independently represent hydrogen or linearor branched (C₁ to C₁₀) alkyl, with the proviso that at least one of R¹³to R¹⁶ is (C₁ to C₁₀) alkyl and r is an integer from 0 to
 5. 19. Thecomposition of claim 18 wherein the said polymer comprises repeatingunits represented by the following structures:

R represents hydrogen or linear and branched (C₁ to C₁₀) alkyl, m and m′idependently represent an integer from 0 to 5 and n is an integer from 0to 10, R* represents a moiety that is cleavable by a photoacid initiatorselected from the group consisting of —C(CH₃)₃, —Si(CH₃)₃, isobornyl,2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranyl,3-oxocyclohexanyl, mevalonic lactonyl, dicyclopropylmethyl anddimethylpropylmethyl.
 20. The composition of claim 19 wherein m is 0, m′is 1, and n is
 0. 21. The composition of calim 20 wherein said polymercomposition comprises repeating units represented as follows:


22. The polymer of claim 17, 18, 19, 20, or 21 wherein the unsaturationin the backbone of said polymer is hydrogenated in excess of 90 percent.23. The polymer of claim 22 wherein the unsaturation in the backbone ofsaid polymer is hydrogenated in excess of 95 percent.
 24. The polymer ofclaim 23 wherein the unsaturation in the backbone of said polymer isessentially 100 percent hydrogenated.
 25. The composition of claim 1, 2,3, 4, 5, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or 21 wherein saidpolymer contains 5 to 100 mole % of repeating units containing said acidlabile groups.
 26. The composition of claim 25 wherein said polymercontains 20 to 90 mole % of repeating units containing said acid labilegroups.
 27. The composition of claim 26 wherein said polymer contains 30to 70 mole % of repeating units containing said acid labile groups. 28.The composition of claim 24 wherein said polymer contains 5 to 100 mole% of repeating units containing said acid labile groups.
 29. A polymercomposition including polymer chains comprising adjacent polycyclicmonomeric units that are linked together in 2,7-repeating unitenchainment, at least some of said polycyclic units having pendanttertiary butylesters of carboxylic acid.
 30. The polymer composition ofclaim 29 comprising repeating units of tert-butylester of 5-norbornenecarboxylic acid.
 31. The polymer composition of claim 29 comprisingrepeating units of the tert-butylester of 5-norbornene carboxylic acidand the linear (C₁ to C₅) alkyl ester of 5-norbornene carboxylic acid.32. A polymer composition comprising polymer chains having repeatingunits represented as follows:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)—OC(O)OR, —(CH₂)_(n)—C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂,subject to the proviso that at least one of R¹ to R⁴ is selected fromthe acid labile group —(CH₂)_(n)—C(O)OR*, R represents hydrogen orlinear and branched (C₁ to C₁₀) alkyl, m is an integer from 0 to 5 and nis an integer from 0 to 10, and R* represents a moiety that is cleavableby a photoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl,dicyclopropylmethyl, and dimethylpropylmethyl, R** independentlyrepresents R and R*.
 33. The composition of claim 31 wherein saidpolymer further comprises at least one repeating unit selected from thegroup represented as follows

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl monocyclic and polycyclic (C₄ to C₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to10; R⁹ to R¹² independently represent hydrogen, linear and branched (C₁to C₁₀) alkyl and a carboxylic substituent represented by the formula—(CH₂)_(n)C(O)OH, with the proviso that at least one of R⁹ to R¹² is acarboxylic substituent, q is an integer from 0 to 5, and n is an integerfrom 0 to 10; and R¹³ to R¹⁶ independently represent hydrogen or linearor branched (C₁ to C₁₀) alkyl, with the proviso that at least one of R¹³to R¹⁶ is (C₁ to C₁₀) alkyl, and r is an integer from 0 to
 5. 34. Thepolymer composition of claim 33 comprising repeating units having thefollowing structures:

wherein m and p independently represent 0 or 1, R* represents a moietythat is cleavable by a photoacid initiator selected from the groupconsisting of —C(CH₃)₃, —Si(CH₃)₃, isobornyl 2-methyl-2-adamantyl,tetrahydrofuranyl, tetrahydropyranyl, 3-oxocyclohexanyl, mevaloniclactonyl dicyclopropylmethyl and dimethylpropylmethyl and R′ representsthe group (CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OC(O)R″, —(CH₂)_(n)OC(O)OR″,where n independently is 0 to 5, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl, monocyclic and polycyclic (C₄ to C₂₀)cyclo-aliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers.
 35. The polymer of claim 34 comprising repeating units havingthe following structures:

wherein R⁸ represents the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, n is 0 to 5, and R″ represents hydrogen linear (C₁to C₁₀) alkyl.
 36. The polymer of claim 35 wherein R⁸ is C(O)OR″ whereinR″ is selected from the group consisting of methyl, ethyl, propyl, butyland pentyl.
 37. The polymer of claim 29, 30, 31, 32, 34, 35, or 37wherein said polymer has a pendant perfluorophenyl group at least oneterminal end thereof.
 38. A polymer produced by polymerizing a monomercomposition comprising a polycyclic monomer and a solvent in thepresence of a single component catalyst having the formula:E_(n)Ni(C₆F₅)₂ wherein E is a neutral 2 electron donor ligand and n is 1or 2, and wherein said polycyclic monomer is selected from a monomerhaving the following formula:

wherein R¹ to R⁴ independently represent a substituent selected from thegroup consisting of hydrogen, linear and branched (C₁ to C₁₀) alkyl, andthe group —(CH₂)_(n)—C(O)OR*, —(CH₂)_(n)—C(O)OR, —(CH₂)_(n)—OR,—(CH₂)_(n)—OC(O)R, —(CH₂)_(n)—OC(O)OR, or —(CH₂)_(n)—C(O)R,—(CH₂)_(n)C(R)₂CH(R)(C(O)OR**), and —(CH₂)_(n)C(R)₂CH(C(O)OR**)₂,subject to the proviso that at least one of R¹ to R⁴ is selected fromthe acid labile group —(CH₂)_(n)—C(O)OR*, R represents hydrogen orlinear and branched (C₁ to C₁₀) alkyl m is an integer from 0 to 5 and nis an integer from 0 to 10, and R* represents a moiety that is cleavableby a photoacid initiator selected from the group consisting of —C(CH₃)₃,—Si(CH₃)₃, isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl,tetrahydropyranyl, 3-oxocyclohexanyl, mevalonic lactonyl,dicyclopropylmethyl, and dimethylpropylmethyl, R** independentlyrepresents R and R*.
 39. The polymer of claim 38 wherein said monomercoposition further comprises a polycyclic monomer of the formula:

wherein R⁵ to R⁸ independently represent a neutral substituent selectedfrom the group —(CH₂)_(n)C(O)OR″, —(CH₂)_(n)—OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, —(CH₂)_(n)—C(O)R″, —(CH₂)_(n)C(R)₂CH(R)(C(O)OR″),and —(CH₂)_(n)C(R)₂CH(C(O)OR″)₂, wherein R represents hydrogen or linearand branched (C₁ to C₁₀) alkyl, R″ represents hydrogen or linear andbranched (C₁ to C₁₀) alkyl monocyclic and polycyclic (C₄ toC₂₀)cycloaliphatic moieties, cyclic esters, cyclic ketones, and cyclicethers subject to the proviso that when R″ is hydrogen at least one ofthe remaining R⁵ to R⁸ groups contains a substituent where R″ is (C₁ toC₁₀) alkyl, p is an integer from 0 to 5, and n is an integer from 0 to10.
 40. The polymer of claim 39 wherein said monomer compositioncomprises monomers of the formulae:

wherein R⁸ represents the group —(CH₂)_(n)—C(O)OR″, —(CH₂)_(n)—OC(O)R″,—(CH₂)_(n)—OC(O)OR″, n is 0 to 5, and R″ represents hydrogen linear (C₁to C₁₀) alkyl.
 41. The polymer of claim 38, 39, or 40 comprising 2,7-linked polycyclic repeating units.
 42. The polymer of claim 1, 2, 38,39, 40, or 41 wherein said polymer has a pendant perfluorophenyl groupat least one terminal end thereof.
 43. The polymer of claim 38 wherein nis 1 and ligand E in said catalyst composition is selected from thegroup consisting of benzene, mesitylene, and toluene.
 44. The polymer ofclaim 38 wherein n is 2 and ligand E in said catalyst composition isselected from the group consisting of THF, dioxane, and diethylether.45. A photoresist composition comprising a photoacid initiator, anoptional dissolution inhibitor, and a polymer including polymer chainscomprising adjacent polycyclic monomeric units that are linked togetherin 2,7-repeating unit enchainment, at least some of said polycyclicunits having pendant tertiary butylesters of carboxylic acid or acopolymer thereof.
 46. The photoresist composition of claim 45 whereinsaid polymer comprises repeating units of the tert-butylester of5-norbornene carboxylic acid and the linear (C₁ to C₅) alkyl ester of5-norbornene carboxylic acid.